TWI266752B - Silica sol containing titanium and manufacturing method thereof, antifouling film, base material with ink receptive layer, and regeneration method of base material for recording - Google Patents

Silica sol containing titanium and manufacturing method thereof, antifouling film, base material with ink receptive layer, and regeneration method of base material for recording Download PDF

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TWI266752B
TWI266752B TW094130047A TW94130047A TWI266752B TW I266752 B TWI266752 B TW I266752B TW 094130047 A TW094130047 A TW 094130047A TW 94130047 A TW94130047 A TW 94130047A TW I266752 B TWI266752 B TW I266752B
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Taiwan
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titanium
sol
porous
integer
receiving layer
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TW094130047A
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TW200619145A (en
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Manabu Watanabe
Tatsuo Ogawa
Hiroyasu Nishida
Michio Komatsu
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Catalysts & Chem Ind Co
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/149—Coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • C09C1/3054—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01—INORGANIC CHEMISTRY
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    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
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    • C08K9/00—Use of pretreated ingredients
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Dispersion Chemistry (AREA)
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  • General Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Silicon Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

The object of the present invention is to provide an antifouling film which is convenient to use on a base material, adapted to be used on wide material and with excellent antifouling performance, and a material which may be used to form a base material with ink receptive layer having excellent decolorization performance. The silica sol containing titanium is characterized by consisting of: (a1) titania particles with average particle size of 2 to 50 nm and porous silica particles with average particle size of 5 to 100 nm and specific surface area of 300 m<2>/g when estimated by BET method, or (a2) porous silica particles having average particles size of 5 to 100 nm and specific surface area of more than 300 m<2>/g when estimated by BET method, the surface thereof modified with a titanate compound; and a dispersing medium.

Description

11266752 九、發明說明： 【發明所屬之技術領域】 本發明係有關構成從船底、天花板材料到糊紙拉門等 廣範圍適用之抗污被膜形成用組成物原料之微粒子，詳古 之，為適用於在金屬、玻璃、木材、塑料、陶究、紙類^ 、、且成之基材表面形成抗污被膜組成物之原料之含有鈦之石 溶膠及其製造方法。 本發明亦有關在PET、氯化乙稀等樹脂製薄膜、紙、 純、布等印刷使用之基材上形成墨水接受層之附有墨水 接文層之基材等。本發明又有關記錄用基材之再生方法。 【先前技術】 / 船底、漁網等水中構造物，由於長時期在水中，尤其 在海水中使用’該水中構造物與海水等之接觸部分將附著 亚繁殖以綠草（綠藻植物）等為代表之多數海中生物，導至 船舶之燃料效率降低或漁網等原本之機能降低。[Technical Field] The present invention relates to a fine particle constituting a material for forming a composition for a wide range of anti-fouling film formations, such as a ship bottom, a ceiling material, and a paper-sliding door. A titanium-containing stone sol which is a raw material for forming a stain-resistant coating composition on a surface of a substrate made of metal, glass, wood, plastic, ceramics, paper, or the like, and a method for producing the same. Further, the present invention relates to a substrate having an ink receiving layer in which an ink receiving layer is formed on a substrate made of a resin such as PET or chlorinated resin, paper, pure cloth or cloth. The invention further relates to a method of regenerating a substrate for recording. [Prior Art] / Underwater structures such as bottoms and fishing nets are represented by green grass (green algae plants) due to the use of 'the underwater structure and the seawater in the sea for a long period of time. Most of the marine organisms lead to a reduction in the fuel efficiency of the ship or the original function of the fishing net.

.，、、了解決該等問題’以防止海中生物附著為目的， 船底或漁網等表面適合使用抗污劑。具體而言在有機抗污 劑中配合為了將抗污劑適當溶出之水解性樹脂等載色劑之 m组成物廣泛被使用。具有抗污性之載色劑例 ^匕”橡膠等可作為抗污劑使用。但是，該等抗污劑Γ 成物不能獲得可滿足之抗污性。 “ —姑=1屬、木材、塑料及紙類被廣泛使用作為以天 :板r料、，材、床材、糊紙拉Η為首之種種材料，但是， &lt;用會附者以塵埃、油煙、皮脂等為主之有機系污垢物 317388 5 ^ 1266752 • &gt; 一質，當初之色彩有消色之傾向。以使附著於該等材料表面 之污垢容易分解為目的之提案，有例如於該等材料預先塗 覆氟素樹脂之方法、以及塗佈矽樹脂、丙烯酸樹脂、胺基 曱酸酯樹脂或氟素系塗料等方法。 於專利文獻1(特開2001-72869號公報）揭示具有聚矽 氧烷嵌段、丙烯酸樹脂嵌段、以及以 -M-0C〇-(GCOO)r-(CH2)p-[M 表示 2 價金屬原子，G 表示 2 價烴基’r表示0或l，p表示〇至5之整數]表示之含有金 丨屬之結合基，上述含有金屬之結合基可存在於上述聚矽氧 烧嵌段與丙烯酸樹脂錢之間；歧由存在於上述丙婦酸 ，脂喪段巾具有特定極限減[η]之錢共聚物，以及上述 嵌段共聚物構成之抗污被卿成用組成物。根據該抗污被 =成用組成物’可在漁網等基材表面形成對於藻類、殼 菜等貝類等之水中生物顯示優越抗污性之塗膜。根據專利 文獻1揭不之基材抗污處理方法，經由在與海水接觸之基 ^表面〜貝、塗佈上述抗污劑組成物’在不會引起環境污 ^下可有效率地形成被膜。 :專利文獻2(4寸開2001-19848 ?虎公報）揭示有關於含 特定親水性親油性平衡範圍之聚環氧烧改質石夕之抗污 =^成用組成物之發明，根據該文獻揭示之基材抗污處 膜m在m該水接觸之基材表面或適用該抗污被 有心1且成物之漁具、漁網、水中構造物等之表面，可 有效防止藻類等之附著。 於專利文獻3 (特開平9-227804號公報）揭示含有由具 317388 6 r 1266752 I i 有聚氟炫基之丙烤酸醋及/或具有聚氣烧基之？基酸 甲醋聚合而成之單位之聚合物、以及在水性溶劑中含有未 含異氰酸醋基之聚胺基甲酸醋化合物之抗污效果優越之涂 覆劑。根據該抗污塗覆劑，可由簡便之處理方法在基材^ 面形成對於種種污垢具有優越抗污性之被膜，獲得之被膜 不僅具有抗污性，從硬度及外觀之點而言亦優越。 專利文獻4(特開2__34422號公報）揭示有在執硬化 性聚合型不飽和酯中使存在二環己基碳化二亞胺，對特定 之夕树月曰接枝來合而成之樹脂材料作為水性污垢附著防止 ㈣明。將由該水性污垢附著防止樹刪 膜^鼠酉夂酉曰化合物製得之硬化物作為水性污垢之抗污被 化神ft獻5(特開2隊342359號公報）揭示關於由熱硬 膜之飽和醋與石夕樹脂之接枝聚合物構成之抗污被. . . , to solve these problems 'to prevent the attachment of organisms in the sea, the surface of the bottom of the ship or fishing nets is suitable for the use of anti-fouling agents. Specifically, an organic antifouling agent is used in combination with a vehicle composition such as a hydrolyzable resin which is appropriately eluted from the antifouling agent. A vehicle having antifouling properties can be used as an antifouling agent. However, such antifouling agents cannot obtain a stain resistance which can be satisfactorily. "—姑属1, wood, plastic And papers are widely used as various materials including: r-materials, materials, bed materials, and paper-making materials. However, &lt;organic materials containing dust, soot, sebum, etc. 317388 5 ^ 1266752 • &gt; A quality, the original color has a tendency to eliminate color. For the purpose of easily decomposing the dirt adhering to the surface of the materials, there are, for example, a method of pre-coating a fluorine resin on the materials, and coating a resin, an acrylic resin, an amino phthalate resin or a fluorine. A method such as coating. Patent Document 1 (JP-A-2001-72869) discloses a polyoxyalkylene block, an acrylic resin block, and a -M-0C〇-(GCOO)r-(CH2)p-[M represents a 2 valence a metal atom, G represents a divalent hydrocarbon group 'r represents 0 or 1, and p represents an integer of 〇 to 5, and represents a bond group containing a metal ruthenium, and the above metal-containing bond group may be present in the above polyoxy oxyalkylene block and Between the acrylic resin money; the difference between the above-mentioned propylene glycol, the fat smear towel has a specific limit minus [η] of the money copolymer, and the block copolymer composed of the anti-staining composition. According to the anti-fouling composition, a coating film which exhibits superior stain resistance to aquatic organisms such as algae or shellfish can be formed on the surface of a substrate such as a fishing net. According to the substrate antifouling treatment method disclosed in Patent Document 1, the film can be efficiently formed by applying the above-mentioned antifouling agent composition to the surface which is in contact with seawater without causing environmental pollution. : Patent Document 2 (4 inch open 2001-19848? Tiger Bulletin) discloses an invention relating to a composition of a polyepoxy-fired modified stone having a specific hydrophilic lipophilic balance, according to the composition The substrate anti-fouling film m disclosed can effectively prevent the adhesion of algae or the like on the surface of the substrate which is in contact with the water or on the surface of the fishing gear, the fishing net, the underwater structure or the like which is suitable for the antifouling. It is disclosed in the patent document 3 (Japanese Laid-Open Patent Publication No. Hei 9-227804) that it contains an acrylic acid vinegar having a polyfluoronon group of 317388 6 r 1266752 I i and/or a polygas group. A polymer of a unit obtained by polymerizing methyl acetonate and a coating agent containing a polyaminocarbamic acid acetate compound not containing an isocyanate group in an aqueous solvent. According to the antifouling coating agent, a film having superior antifouling properties against various kinds of soils can be formed on the surface of the substrate by a simple treatment method, and the obtained film not only has antifouling properties, but also is excellent in terms of hardness and appearance. A resin material obtained by grafting and combining a dicyclohexylcarbodiimide in a curable polymerizable unsaturated ester in a curable polymerizable unsaturated ester is disclosed in the patent document 4 (JP-A No. 2-34422). Prevent dirt adhesion (4). The hardened material obtained by the water-based soil adhesion prevention tree-removing hamster compound is used as an anti-staining agent for water-based soils, and it is disclosed by the hot hard film. Anti-fouling agent composed of graft polymer of vinegar and Shixi resin

Si: :將該樹脂材料塗怖於金屬、合成樹脂、木材、 或玻璃等基材，則有機溶劑蒸發飛散後可形成抗污被 專利文獻6(特開2〇〇〇_ΐ92〇21 _八- ^ 基材表面之金屬氧μ報）揭不關於包覆於 —之凹凸係以在高度方向具有25至 之親水性·抗計&quot;亏^ 1〇0微米之表面形狀為特徵 高、透明性優越，且叙過具:屬乳化物被膜硬度 親水性·抗霧抗污基材之;可污性能。該等 溶劑中添加形成某材用^ 係在基材表面塗佈在 基材用之有機金屬化合物及顯示吸水性及 317388 7 ^ 1266752 $ /或光催化活性之超微粒子拌 進行水解、&amp;取_ 欖拌、混合之溶液，使 好矣而 反應後乾燥·燒成⑽至70(TC)，而^ 材表面形成1右# ^ ^ 王/υυ丄），而在基 但日成:、有規則性凹凸之金屬氧化物被膜之方法。 疋’月望有在基材之適用方、、表μ # 圍之基材mm 方法間便、可適用於廣範 現。 成有叙越抗污性能之抗污被膜之材料出 印刷戋昭像方 方弋之「刷為可狻得與以往多色 丨m、像方式相同晝質之 在印刷份數少日丰甘4、士 五谷易同速化、多色化， 種用途。bn j 往之印刷方法低，f及於種 等紙類或OHP片箄㈣，丨詩P /為日通紙、的用紙 片#印刷基材大1消費之原因之一。 ==獻7(特開__27()225號公報)揭示在載體上 ΓίΓ 層而形成之喷墨記錄介質，以該墨水接受声 :屬ί=不二ί化·之氧化鋅、氧化鈦等過渡 之平均2 Γ 4不定形二氧化發包覆之過渡金屬氧化物 對於二/人粒徑在2.〇/^以上8.〇&quot;m下為特徵之技術， 、：以&quot;f墨d錄介質具有優越耐光性亦有揭示。 專利文獻8(特開200心237538號公報）揭示至少在載 體f設置經由加入熱能而形成發色狀態及消色狀態之可逆 性圯錄層，係經由外加熱能可從載體表面視認在該可逆性 記錄層形成之發色圖像使用之可逆性記錄介質，在該記錄 層形成之圖像在從上述㈣可認識之程度下，載體具透明 性且赫茲值在90%以上為特徵之可逆性記錄介質之發明。 在該記錄層或隱蔽層使含有氧化鈦，可形成鮮明之圖像。 317388 8 於專利文獻9(專利第3,313,3ί9號公報）揭示有關將由 平均粒控0.05 1 〇.2//m之氧化欽微粒+、水解性石夕化人 物或該耗合物之水解物及/或水解性魏合物之部㈣ 合物、以及溶齡叙透明㈣組絲塗抹於基材上 字部分之色料使用經紫外線照射可消色之染料組成之墨水 組成物進行印刷’由此獲得之印刷物用紫外線照射即可將 印字部分消色所構成之印刷基材再生方法之相關發明。Si: : The resin material is coated on a substrate such as metal, synthetic resin, wood, or glass, and the organic solvent evaporates and scatters to form an antifouling patent document 6 (Special opening 2〇〇〇_ΐ92〇21 _8 - ^ Metal Oxygen on the Surface of the Substrate) The surface of the surface of the substrate is characterized by a high degree of transparency and transparency. It is superior in character and has the following characteristics: it is a polyurethane membrane hardness hydrophilic, anti-fog and anti-fouling substrate; These solvents are added to form a certain material, and the organometallic compound for coating the substrate on the surface of the substrate and the ultrafine particles exhibiting water absorption and 317388 7 ^ 1266752 $ / or photocatalytic activity are mixed and hydrolyzed. _ 榄 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , A method of regularly forming a metal oxide film of irregularities.疋 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月 月The material of the anti-fouling film that has the anti-fouling performance of the anti-fouling performance is printed. 戋 像 方 方 方 「 「 「 「 「 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷 刷, Shiba Valley easy to speed, multi-color, a variety of uses. bn j to the low printing method, f and other kinds of paper or OHP film (four), 丨 po P / for the Japanese paper, the use of paper # printing One of the reasons why the substrate is consumed by a large one. == 7 (Unexamined __27() 225) discloses an inkjet recording medium formed by laminating a layer on a carrier, and accepting sound with the ink: ί=不The average transition of the zinc oxide, titanium oxide, etc., is 2 Γ 4 The amorphous metal oxide coated transition metal oxide is characterized by a particle size of 2. 〇 / ^ above 8. 〇 &quot; m The technique of the present invention is also disclosed in the publication of the &lt;f ink recording medium having a superior light resistance. Patent Document 8 (JP-A-200 237538) discloses that a coloring state and achromatic color are formed at least in the carrier f via the addition of thermal energy. The reversible recording layer of the state is capable of visually recognizing the color image formed on the reversible recording layer from the surface of the carrier via external heating A reversible recording medium in which an image formed on the recording layer is a reversible recording medium characterized by transparency and a Hertz value of 90% or more in a degree recognizable from the above (4). In the recording layer or concealment The layer contains titanium oxide to form a sharp image. 317388 8 Patent Document 9 (Patent No. 3,313, 3 ί9) discloses that the oxidized granules of the average particle size of 0.05 1 〇.2//m are hydrolyzable. The color of the Shi Xihua character or the hydrolyzate of the consumable and/or the hydrolyzed Wei compound (four), and the color of the immersed transparent (four) silk coated on the substrate can be eliminated by ultraviolet irradiation. The ink composition of the dye composition is printed, and the printed article obtained by the ultraviolet ray irradiation can be used to reproduce the printing substrate.

t1266752 但是，期待能有更優越之消色技術出現。 專利文獻1 ··特開2001_72869號公報 專利文獻2 ·特開2001-19848號公報 專利文獻3 ··特開平9-227804號公報 專利文獻4 :特開2〇〇〇_34422號公報 專利文獻5 :特開2000-342359號公報 專利文獻6 ··特開2000-192021號公報 專利文獻7 :特開2〇〇1-27〇225號公報 專利文獻8 ··特開2〇〇4-237538號公報 專利文獻9 ··專利3,313,319號公報 【發明内容】 [發明之揭示] [發明解決課題] 本唤明為換解決上述問題點之發明，以提供對基材之 適用方法簡便、適用於廣泛基材、且可形成具有優越抗污 性能之抗污被膜之材料為目的。 本發明亦以提供可將經由喷墨印刷等之印字或印圖消 317388 9 1266752 • · 色之附有墨水接受層之基材及其製造方法為目的。 本|明又讀已經印字或印圖之印刷用之 成為可能為目的。 [知決課題之方法] 案&amp;月人等為了解決上述課題，經過深人研究之結 子若使用，定之微粒子，亦即使用含有二氧化鈦微J 夕孔質一氧化石夕微粒子（al)或經鈦酸醋系化合物進行 =面修飾所成之多孔f二氧切微粒子（a2)之㈣膠，則 完成之抗污被膜及消色性優越之墨水接受層，因而 本發明之含有鈦之矽溶膠係以由 (a)以下之微粒子（al)或微粒子（a2); 平均粒徑為2至I之二氧化鈦微粒子及平均 ) 至1〇0·經由BET法求得之比表面積在3〇〇m2 /g以上之多孔質二氧化矽微粒子； (a2).平均粒徑為5至1〇〇細，經由贿法求得之 表面積在3〇〇mVg以上之多孔質二氧化石夕微粒子表面用 :酸醋系化合物進行表面修飾所成之多孔質二氧化二 子；以及 ^ (b)分散溶劑； 所組成為特徵。 上述鈦酸酯 項表示者： 系化合物較佳為下述通式（1)至（3)任何一 ⑴ RUnTiR12 317388 10 1266752 [其中，n為1至4之整數 RU為碳原子數1至6之烩_ * 可結合形成下述通式(la)表示之二：物 j(la)中鄰接氧原子之碳原子之—之2個氫原子以氧原 子取代2,形成下述通式（lb)表示之環狀構造； R12為碳原子數1至5之烴基或下述通式（lc)、（ld)、 (le)、（If)、（Ig)或（lh)表示之有機基； [化1] H2?—Ο 〜 (la) (lb) (lc) H2xCx—0〆 (其中’x為1至7之整數） [化2] 0=〒一〇〜T1266752 However, it is expected that there will be more superior achromatic technology. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. JP-A-2000-132359, JP-A-2000-192021, JP-A-2000-192021, JP-A No. 2000-192021 [Patent Document 9] Patent No. 3,313,319 [Disclosure of the Invention] [Disclosure of the Invention] [Dissolution of the Invention] This invention is intended to solve the above problems, and to provide a method for applying to a substrate, which is simple and suitable for a wide range of applications. The material and the material of the anti-fouling film having superior anti-fouling properties are formed. The present invention also aims to provide a substrate to which an ink receiving layer is attached by printing or printing of ink jet printing or the like and a method for producing the same. This is a possible use for printing that has been printed or printed. [Methods for Knowing the Problem] In order to solve the above problems, the people who have been studied by the in-depth study, if used, determine the fine particles, that is, the titanium dioxide micro-J-containing smectite-type nitric oxide particles (al) or The titanate-based compound is subjected to the (four) gel of the porous f-dioxy-cut microparticles (a2) formed by the surface modification, and the finished anti-fouling film and the ink-receiving layer having excellent decolorizing property, and thus the titanium-containing cerium sol of the present invention. The specific surface area obtained by the BET method is 3 〇〇 m 2 / (a) or microparticles (a2); (2) titanium dioxide microparticles having an average particle diameter of 2 to 1 and an average of 1 〇 0. Porous cerium oxide microparticles of g or more; (a2). The average particle diameter is 5 to 1 〇〇, and the surface of the porous TiO2 surface having a surface area of 3 〇〇 mVg or more is obtained by bribery: acid a porous dioxide formed by surface modification of a vinegar-based compound; and (b) a dispersing solvent; characterized by a composition. The titanate terminator is represented by the following formula: (1) RUnTiR12 317388 10 1266752 [wherein n is an integer RU of 1 to 4, and the number of carbon atoms is 1 to 6烩_* may be combined to form two of the following formula (la): two hydrogen atoms of the carbon atom adjacent to the oxygen atom in the substance j(la) are substituted with an oxygen atom by 2 to form the following formula (lb) The cyclic structure represented by R12 is a hydrocarbon group having 1 to 5 carbon atoms or an organic group represented by the following formula (lc), (ld), (le), (If), (Ig) or (lh); 1] H2?—Ο~ (la) (lb) (lc) H2xCx—0〆 (where 'x is an integer from 1 to 7) [Chemical 2] 0=〒一〇~

HjyCy (其中，y為1至7之整數） [化3] ΟHjyCy (where y is an integer from 1 to 7) [Chemical 3] Ο

η II Ο—C—CpH2p+1 (其中，Ρ為4至30之整數） 317388 11 &lt; 1266752 ，[化 4]η II Ο—C—CpH2p+1 (where Ρ is an integer from 4 to 30) 317388 11 &lt; 1266752 , [Chem. 4]

ΟII οΟII ο

Ό—Ρ-—〇-—p-j-o—CqH2q+1 ] 2 OH (Id) (其中，q為4至30之整數），[化5] ΟΌ—Ρ-—〇-—p-j-o—CqH2q+1 ] 2 OH (Id) (where q is an integer from 4 to 30), [Chemical 5] Ο

O Cq fH2q (其中，q’為4至30之整數），[化6] —OCrH2rNHCr，H2r，NH2 (le) (If) (其中，r及r’各為1以上之整數，r+r’為4至30)， [化7]O Cq fH2q (where q' is an integer from 4 to 30), [Chem. 6] - OCrH2rNHCr, H2r, NH2 (le) (If) (where r and r' are each an integer of 1 or more, r + r' 4 to 30), [Chem. 7]

CsH2s+1 (lg) (但是，s為1至30之整數）， 12 317388 1266752 [化8]CsH2s+1 (lg) (however, s is an integer from 1 to 30), 12 317388 1266752 [Chem. 8]

(lh) (值是， t及t，各為！至30之整數）] R21TiR22R232 ...........(2) L式中，p2l、 為碳原子數1至4之烧氧基，R22為下述通式（2a) 表示之士 有機基，R23為下述通式（2b)表示之有機基； L化9] Ο(lh) (value is, t and t, each is! to an integer of 30)] R21TiR22R232 ........... (2) In the formula L, p2l, is a carbon number of 1 to 4 The oxy group, R22 is an organic group represented by the following formula (2a), and R23 is an organic group represented by the following formula (2b); L 9] Ο

II (2a) C—CuH2u+1 (其中，、 u為4至30之整數）， ί化 10] Ο R，II (2a) C—CuH2u+1 (where, u is an integer from 4 to 30), ί 10] Ο R,

—〇Jl I (2b) °〜c—c=ch2 (^、中’ R為氫原子或碳原子數1至4之烷基）]; ^ R314Ti · [P(〇C2wH2w+1)2(〇H)]2 ...........(3) [式中’ R31為碳原子數！至2〇之烷氧基，該烷氧基中氫原 子之一部分可經碳原子數為4至12、具有醚鍵及雙鍵中之 至少一者之有機基取代； w為4至2 0之整數]。 13 317388—〇Jl I (2b) °~c—c=ch2 (^, where 'R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)]; ^ R314Ti · [P(〇C2wH2w+1)2(〇 H)]2 ...........(3) [wherein R31 is the number of carbon atoms! Alkoxy group to 2, a part of a hydrogen atom in the alkoxy group may be substituted with an organic group having 4 to 12 carbon atoms and having at least one of an ether bond and a double bond; w is 4 to 20 Integer]. 13 317388

• I ♦1266752 (a 1) 二二f，鈦微粒子及多孔質二氧切微粒子 :、工处、’酉夂酯系化合物進行表面 二氧切微粒子㈣之㈣之含量，以二斤 比換算’以在5至21，_範圍較佳。咏’⑽重！ 上述多孔質二氧化矽微粒子之 子每在心⑽叫範圍較佳。讀1，以該❹ 氧化ίί二氧化石夕微粒子，以將溶膠狀之二氧化石夕-虱化鋁糸一虱化矽微粒子表面 脫銘處理形成者龍。 &amp;切包覆，接者進行 本矣月之由上述二氧化鈦微粒子矜 :=及：散溶_組成之含有二= H錄子㈣散溶_)構成之鈦轉，與平均粒徑為 I、經由BET法求得之比表面積在3〇0mVg以 / = = 子及分散溶劑_成之石夕溶膠 化人2 2^之上述多孔質二氧化石夕微粒子表面由欽酸醋系 之：二i t散溶劑⑻構成之含有鈦之石夕溶膠㈣ 由：eW其特徵為：在由平均粒徑為5至100nm、經 法求得之比表面積在·mVg以上之多孔質二氧 粒子及分散溶_構成之#膠中添加鈦酸 化合物。 本發明之抗污被膜形成用組成物，其特徵為：在含有 上述鈦之矽溶膠中分散黏合劑（c)。 317388 14 ，1266752• I ♦1266752 (a 1) Two or two f, titanium microparticles and porous dioxygen microparticles:, the content of the surface of the dioxin-cutting compound (4), and the conversion of the bismuth ester compound It is preferably in the range of 5 to 21, _.咏’(10) heavy! The above-mentioned porous cerium oxide microparticles have a preferred range in the center (10). Reading 1, the ❹ ί ί 二 二 二 夕 , , , , , , , , , , 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 &amp;Cut coating, the titanium oxide consisting of the above-mentioned titanium dioxide fine particles =:= and: dissolving _ consisting of two = H recorded (four) dissolving _), with an average particle diameter of I, The specific surface area determined by the BET method is 3 〇 0 mVg / / = = and the dispersion solvent _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The dispersing solvent (8) is composed of a Titanium sol containing titanium (IV). The eW is characterized by: porous dioxygen particles having a specific particle diameter of 5 to 100 nm and having a specific surface area of more than · mVg and dispersed dispersion. A titanate compound is added to the #胶. The antifouling film-forming composition of the present invention is characterized in that the binder (c) is dispersed in a cerium sol containing the above titanium. 317388 14 ,1266752

I I ~ 本發明之墨水接受層形成用塗抹液，以在上述含有鈦 之石夕溶膠中分散黏合劑（C’）而成為特徵。 本發明之墨水接受層形成用塗佈液，以 含有上述微粒子（al)或上述微粒子（a2)100重量份及上 述黏合劑（c’）5至7重量份、 上述分散溶劑（b)之重量（WB)與上述微粒子（al)或上述 微粒子（a2)及上述黏合劑（c’）之合計重量（WA+WC)之比為 WB ·· (WA+WC)=99.9 至 50 : 0·1 至 50[合計為 100]、 • 構成上述微粒子（al)或上述微粒子（a2)之矽及鈦之含 量以Si02/Ti02重量比換算，以5至21,000範圍者較佳。 本發明之墨水接受層形成用塗佈液之第1製造方法， 以將上述二氧化鈦微粒子及多孔質二氧化矽微粒子（a 1)分 散於上述分散溶劑（b)而成之含有鈦之石夕溶膠（a 1 s)、黏合劑 (c’）、以及必要時之上述分散溶劑（b)混合為特徵。 本發明之墨水接受層形成用塗佈液之第2製造方法， I以將上述表面用鈦酸酯系化合物進行表面修飾而成之多孔 質二氧化矽微粒子（a2)分散於上述分散溶劑（b)而成之含有 鈦之矽溶膠（a2s)、黏合劑（c’）、以及必要時之上述分散溶 劑（b)混合為特徵。 本發明之附有墨水接受層之記錄用基材，其特徵為·· 在基材表面形成墨水接受層，該墨水接受層含有（al)上述二 氧化鈦微粒子及多孔質二氧化矽微粒子；或（a2)多孔質二氧 化矽微粒子之表面用鈦酸酯系化合物進行表面修飾而成者。 本發明之附有墨水接受層之記錄用基材之製造方法， 15 317388 ^1266752 1 i =基材表面㈣上述墨水接受層形成用塗㈣後乾燥為 本發明之記錄用基材之再生方法，以在 =Γ基材上用墨水進行印刷形成印字或印圖後二 ==射、㈣減料聽躺進行料 之消色為特徵。 1 口 [發明效果] •㈣若使用本發明含有鈦之矽溶膠’在金屬、玻璃、木材、 ；Γΐ、Λχ、紙類等表面可簡便地形成抗污被膜，該抗污 被膜旎夠發揮優越之抗污效果。 你用ί抗，讀版被用於船底表面時可抑制綠藻類之附著， 吏：於天I匕板材料、壁材、紙類等表面時，在抗污被膜上 二:：：塵埃、油煙、皮脂等為主之有機系污垢物質， 照射或與酸性氣體接觸，可將基材表面上之污 之、-二二。基材若為壁材或紙類，對用墨水等亂寫亂晝 ，之巧垢可發揮分解效果將污垢除去。 炉而ΪΓ本發明之墨水接受層形成用塗抹液經由塗抹、乾 ;刷等而發明附有墨水接受層之記錄基材上進行喷墨 氣體或臭氧接觸而消除。了-由系外線知射、與酸性 參印Hi Γ明記錄用基材之再生方法，可抑制普通紙、 Ί 、‘、專、、，氏類或〇HP片等印刷基材之大量消費。 【實施方式】 貝 乂下對於本發明含有鈦之矽溶膠及其製造方法、抗 317388 16 1266752 ^ , 污被膜及附有墨水接受芦 &amp; 又智之基材、以及記錄用基材之再生 方法加以詳細說明。 物所明書中之「抗污」若無特別說明，則為防止污垢 物貝附者及將附著之污垢物質分解等兩種意義。 於本説明書，對於印刷在 5 j在附有墨水接文層之記錄用基 材表面之印字或印圖等， 土 射紫外線或與酸性氣體或臭氧 色性 乎丨示去無為「消色」，該等特性稱為「消 i 色性」 溶勝 孔所—t/之3有鈦之⑪溶膠，係由二氧化鈦微粒子及多 2 -乳切微粒子(al)(於本說明書亦稱為「微粒 或=鈦酸㈣化合物將表面修飾丄 (:ΓΠ明書亦稱為「微粒子(a2)」、== ==含有…溶膠之形態，可列舉由: 組成之氧本=粒广及分散溶劑⑻ 膠一以及由表面修質書亦：含有一 分散溶劑（b)組成之含有效切溶膠微粒子⑽及 「含有鈦之石夕溶膠（a2s)」）。，；σ兄明書亦稱為 能量=:用…由紫外線等具有特定 用。二氧化鈦微粒子可為無定形之二„催化作 乳化鈦微粒子或結晶 317388 17 1266752 性之一氧化鈦微粒子之任何 時，其結晶型可為銳鈦 種’為結晶性之二氧化鈦 礦型、金紅石创、 一種，亦可Λ寸笪々、日人 % 皮欽石廣型之任何 微粒子之秒溶 係以鈦轉之㈣與分散❹孔質二氧^❹子， 膠混合。 5至氧化鈦微粒子之平均粒徑為2至、，較佳為 原料: = 塗膜形成用組成物之 々入士 拉位右比5亥耗圍+，則鈦溶膠或本發明 =有鈦之⑦料之分散安定性變差；平均粒徑若比該範 則使用本發明之含有狀0轉形叙抗污被膜之 祕，在適用該抗污被膜之基材表面會產生顏色暗 =外硯變差現象’該二氧化鈦微粒子之光催化機能不能 充分發揮。 將上述含有鈦之料膠作為墨水接受層形成用塗抹液 鲁之原料使用# ’上述—氧化鈦微粒子之平均粒徑若比該範 圍小，則鈦溶朦或含有鈦之石夕溶膠或墨水接受層形成用塗 抹液之分散安定性變差；平均粒徑若比該範圍大，則附有 墨水接受層之記錄用基材表面之透明性降低，在附有墨水 接叉層之記錄用基材表面會產生顏色暗淡等外觀變差現 象，以該二氧化鈦微粒子之光催化機能為基礎之消色效果 不能充分發揮。 ^上述二氧化鈦微粒子之比表面積並無特別限制，只要 平均粒徑在上述範圍之二氧化鈦微粒子即可適用於本發 317388 18 1 1266752 &quot;明。 &quot;—氧化鈦微粒子之粒子性狀並無特別限制，可為球狀 粒子或非球狀粒子之任何一種，亦可為多孔 質粒子。 作為分散有上述二氧化鈦微粒子之鈦溶膠之出發原 =，可使用硫酸鈦、氣化鈦等鈦化合物、結晶型為銳鈇礦 型及/或金紅石型、皮鈦礦型之粉末狀二氧化鈦等。出發 原料使用平均粒徑大於2至5〇nm之鈦化合物或二氧化鈦 籾末牯，將該等粉碎使粒徑變小後使用。該等二氧化鈦粉 末可將市售之超微粒子氧化鈦以原狀或燒成後使用。I I ~ The application liquid for forming an ink receiving layer of the present invention is characterized in that the binder (C') is dispersed in the above-mentioned titanium-containing sol. The coating liquid for forming an ink receiving layer of the present invention contains 100 parts by weight of the fine particles (al) or the fine particles (a2) and 5 to 7 parts by weight of the binder (c'), and the weight of the dispersion solvent (b). The ratio of (WB) to the total weight (WA+WC) of the above fine particles (al) or the above fine particles (a2) and the above-mentioned binder (c') is WB ··(WA+WC)=99.9 to 50:0·1 To 50 [total 100], the content of ruthenium and titanium constituting the fine particles (al) or the fine particles (a2) is preferably in the range of 5 to 21,000 in terms of the weight ratio of SiO 2 /TiO 2 . In the first production method of the coating liquid for forming an ink-receiving layer of the present invention, the titanium dioxide-containing sol is obtained by dispersing the titanium dioxide fine particles and the porous ceria fine particles (a1) in the dispersion solvent (b). The (a 1 s), the binder (c'), and, if necessary, the above-mentioned dispersion solvent (b) are mixed. In the second production method of the coating liquid for forming an ink receiving layer of the present invention, the porous cerium oxide fine particles (a2) obtained by surface-modifying the surface titanate-based compound are dispersed in the dispersion solvent (b). The titanium-containing cerium sol (a2s), the binder (c'), and, if necessary, the above-mentioned dispersion solvent (b) are mixed. The substrate for recording having the ink receiving layer of the present invention is characterized in that: an ink receiving layer is formed on the surface of the substrate, and the ink receiving layer contains (al) the titanium dioxide fine particles and the porous ceria particles; or (a2) The surface of the porous ceria microparticles is surface-modified with a titanate compound. A method for producing a substrate for recording having an ink receiving layer according to the present invention, 15 317 388 ^ 1266752 1 i = substrate surface (4) coating of the ink receiving layer (4) and drying the substrate for recording of the present invention, It is characterized by the use of ink on the substrate to form a printing or printing to form a printing or printing, and then to eliminate the color of the material. 1 [Invention Effect] • (4) When the titanium-containing cerium sol of the present invention is used, a stain-resistant film can be easily formed on the surface of metal, glass, wood, enamel, enamel, paper, etc., and the anti-fouling film is excellent in performance. Anti-fouling effect. You use ί, when the reading plate is used on the bottom surface of the ship, it can inhibit the adhesion of green algae. 吏: When the surface of the 匕 plate, wall material, paper, etc., on the anti-fouling film, two::: dust, soot Organic semen, such as sebum, is irradiated or contacted with acid gas, which can stain the surface of the substrate. If the substrate is made of a wall material or a paper, it may be scribbled with ink or the like, and the fine scale may exert a decomposition effect to remove the dirt. The coating liquid for forming an ink receiving layer of the present invention is invented by applying ink, gas or ozone to a recording substrate having an ink receiving layer by applying, drying, or the like. - A method of regenerating a substrate for recording by an external line and an acidic substrate, which can suppress the mass consumption of printing substrates such as plain paper, Ί, 、, special, 氏, or 〇HP sheets. [Embodiment] The present invention relates to a titanium-containing cerium sol according to the present invention, a method for producing the same, an anti-317388 16 1266752 ^, a smear film, and a substrate for reclaiming a substrate containing the ink, and a recording substrate. Detailed description. Unless otherwise specified, the "anti-fouling" in the book of the object is intended to prevent the decontamination of the dirt and the attached dirt material. In the present specification, for printing or printing on the surface of the recording substrate with the ink interface layer printed thereon, the ultraviolet light or the acidity of the acid gas or the ozone is inconspicuous. These characteristics are called "eliminating color". The melting hole - t / 3 has titanium 11 sol, which is composed of titanium dioxide microparticles and multiple 2 - milk-cut microparticles (al) (also referred to as "particles" in this specification. Or = titanic acid (4) compound surface modification 丄 (: ΓΠ 书 亦 亦 「 「 「 「 微粒 、 、 = = = = = 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶 溶胶Glue 1 and the surface repair book also include: a dispersing solvent (b) containing effective cut sol particles (10) and "titanium-containing sol (a2s) containing titanium). : It is used by ultraviolet light, etc. The titanium dioxide microparticles can be amorphous. When catalyzed as emulsified titanium microparticles or crystal 317388 17 1266752, any of the titanium oxide microparticles, the crystal form can be anatase Titanium dioxide type, rutile, one kind, The second solution of any fine particles of 皮 笪々 日 日 日 皮 皮 以 以 以 皮 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛Preferably, the raw material is: = the composition of the coating film forming composition is lower than the 5 watts of the right side, and the dispersion stability of the titanium sol or the present invention = titanium material is deteriorated; If the diameter is larger than the standard, the secret of the anti-fouling film containing the 0-shaped shape of the present invention is used, and the surface of the substrate to which the anti-fouling film is applied may have a color darkness = a phenomenon of poor external enthalpy. The titanium-containing material paste is used as a raw material for the ink-receiving layer forming application liquid. # 'The above-mentioned titanium oxide fine particles have an average particle diameter smaller than the range, and the titanium solution or the titanium-containing stone The dispersion stability of the coating liquid for forming the sol or the ink receiving layer is deteriorated; if the average particle diameter is larger than the range, the transparency of the surface of the recording substrate with the ink receiving layer is lowered, and the ink bonding layer is attached thereto. The surface of the substrate for recording will produce a dark color The appearance deterioration phenomenon is not sufficiently exhibited by the photocatalytic function of the titanium dioxide fine particles. The specific surface area of the titanium dioxide fine particles is not particularly limited, and any titanium dioxide fine particles having an average particle diameter within the above range can be suitably used. The present invention is not limited to the particle shape of the titanium oxide fine particles, and may be any of spherical particles or non-spherical particles, or may be a porous particle. The origin of the titanium sol of the fine particles = titanium compound such as titanium sulfate or vaporized titanium, powdered titanium dioxide having a crystal form of ruthenium type and/or rutile type or zirconia type, etc. A titanium compound having a diameter of more than 2 to 5 Å or a titanium dioxide ruthenium ruthenium is used, and the pulverization is carried out to reduce the particle diameter. These titanium dioxide powders can be used after the commercially available ultrafine titanium oxide is used as it is or after firing.

本發明使用之二氧化矽微粒子為多孔質二氧化矽微粒 子，亦即比表面積大之二氧化矽微粒子，經由BET法求得 之比表面積在3〇〇m2/g以上，較佳為4〇〇m2/g以上。 3有比表面積在該等範圍之多孔質二氧化矽微粒子及 鈦/合膠之含有鈦之矽溶膠、或含有將該多孔質二氧化矽微 粒子用鈦酸酯系化合物進行表面修飾而成之多孔質二氧化 石^微粒子之含有鈦之矽溶膠組成之抗污被膜，經由紫外線 照射或與酸性氣體接觸，可發揮優越之抗污效果。 由使用含有比表面積在該等範圍之多孔質二氧化矽微 津子及鈦洛餐之含有鈦之石夕溶膠、或含有將該多孔質二氧 化矽U粒子用鈦酸酯系化合物進行表面修飾而成之多孔質 二氧化矽微粒子之含有鈦之矽溶膠組成之墨水接受層形成 用塗抹液而形成之墨水接受層，經紫外線照射或與酸性氣 體接觸’可發揮優越之消色效果。 317388 19 1266752 • * 上述多孔質二氧化石夕微粒子之平均粒徑為5至 lOOnm，較佳為 1〇 至 5〇nm。 含:鈦之靖作為抗污塗膜形成用組成物之 2 一乳切❹子之轉或含有鈦之料膠之分 降低之傾向；平均粒徑若比該範圍大，則使用含有欽之 成之抗污被膜之透明性降低，在形成該抗污被膜 會產生外觀變差現象或與該多孔質二 粒=存之二氧化鈦微粒子之光催化機能不能充分發揮。 二=有:Γ溶穋作為墨水接受層形成用塗佈液 孔平均粒徑若比該範圍小，則分散有上述多 貝一減㈣粒子之轉、含有上㈣ =:,成圍用大塗佈液之— =右比心圍大，則形成之墨水接受層之透明性降低 有墨水接受層之基材外顴綠矣 .% -附 或與料孔質二氧化矽 =子共存之二氧化鈦微粒子之光催化機能為基 效果不能充分發揮。 巴 e二：孔f二氧切微粒子表面電荷量以1〇至、 之原：溶膠作為墨水抗污塗膜形成用組成物 之原科使科，表面電荷量若未滿心叫々，則 亡，多孔質二氧化矽微粒子之溶膠或本發明之含有鈦： 洛膠有不安定之傾向·若_ 性㈣則該溶膠之黏 有'又间傾向’含有以該多孔質二氧切微粒子作為主 317388 20 4 1266752 • , 成分之抗污被膜形成用έ 被膜。 &amp;用、、且成物之黏度亦高，較難形成均一 若使用表面電荷量在 二氧化矽《 ^ 至150#叫々範圍之多孔質 乳化石夕❹子’不僅可形成透 匕貝 ^孔質二氧化卿子之溶膠與鈦溶膠混：=將含有該 亚使乾燥而形成被:▲佈於基材 表面電荷量大，所以溶膠中 匕夕从粒子之The cerium oxide microparticles used in the present invention are porous cerium oxide microparticles, that is, cerium oxide microparticles having a large specific surface area, and the specific surface area determined by the BET method is 3 〇〇 m 2 /g or more, preferably 4 Å. M2/g or more. (3) a porous cerium oxide microparticle having a specific surface area in the above range, a titanium-containing cerium sol having a titanium/gel, or a porous surface obtained by surface-modifying the porous cerium oxide microparticle with a titanate-based compound The anti-fouling film composed of the cerium-containing sol of the fine-grained stone and the fine particles can be excellent in the anti-fouling effect by ultraviolet irradiation or contact with an acid gas. The use of a Titanium-containing sol containing titanium having a specific surface area in the range of the porous ceria and a titanium meal, or a surface modification of the porous ceria U particle with a titanate compound The ink-receiving layer formed of the coating liquid for forming the ink-receiving layer of the porous cerium oxide microparticles of the porous cerium oxide microparticles, which is formed by the irradiation of ultraviolet rays or in contact with an acid gas, exhibits an excellent color erasing effect. 317388 19 1266752 • The above porous silica dioxide particles have an average particle diameter of 5 to 100 nm, preferably 1 to 5 nm. Contains: Titanium as a composition for forming an antifouling coating film 2 The tendency of the milk to cut the tweezers or the content of the rubber containing titanium is reduced; if the average particle size is larger than the range, the use contains The transparency of the anti-fouling film is lowered, and the appearance of the anti-fouling film is deteriorated, or the photocatalytic function of the titanium dioxide microparticles containing the porous particles is insufficient. (2) 有 Γ Γ Γ Γ Γ 穋 穋 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水 墨水The cloth liquid - = right than the core is large, the transparency of the formed ink receiving layer is reduced. The substrate of the ink receiving layer is green 矣.% - titanium dioxide particles with or with the pore-type cerium oxide = sub-existing The photocatalytic function cannot be fully utilized. Bae II: The surface charge of the pores of the fluorinated microparticles is 1 〇 to the original: the sol is used as the composition of the composition for forming the antifouling coating film of the ink. If the surface charge is not full, it will die. The sol of the porous cerium oxide microparticles or the titanium containing the present invention: the rubber has a tendency to be unstable. If the sol (the fourth), the adhesion of the sol has a 'remaining tendency' containing the porous dioxygen microparticles as the main 317388. 20 4 1266752 • , The anti-fouling film of the component is formed into a film. &amp; use, and the viscosity of the product is also high, it is difficult to form a uniform if the surface charge amount in the cerium oxide "^ to 150 # 々 々 之 之 之 多孔 多孔 多孔 多孔 ' ' ' ' ' ' 不仅 不仅 不仅 不仅 不仅 不仅The sol of the porous oxidized sulphur dioxide is mixed with the titanium sol: = it will be dried to form the quilt: ▲ cloth is charged on the surface of the substrate, so the amount of charge in the sol is from the particle

拉子為均-分散狀態而容易形成被膜。 乳化鈦U 將上述含有鈦之溶膠 原料使用時，表面電荷量】t;: 成用塗佈液之 述多孔質二氧化石夕㈣^ q/g ’則分散有上 墨水接受層形成用塗佈有=石夕溶膠或 eq/g，則分4古 、向，右超過150// g貝J刀放有上述多孔質二氧化石夕 有鈦之石夕溶膠之黏性有變高之 ^或該含 溶膠作為主成分之墨水接 3有以“有鈦之矽 高，不易來心 層形成用塗抹液之黏度亦變 门不易形成均一之被膜。 夂 若使用表面電荷量在 二氧化卿子，則可::透:^ 該多孔質二氧化石夕微粒子之接受層。由於 化鈦微粒子成為均—分散狀㉟2❹子不易凝集’二氧 層形成用塗抹液塗佈·乾燥;、成斤^在基材上將墨水接受 鈦撻粒子充分分散。其結果 a -虱化 ffl ^ * 七月之附有墨水接受層之 5己錄用基材發揮良好之消色性。 方土八接又層之 317388 21 1266752 本發明使用之多孔質二氧化石夕 势 特別限制，可適當使用公知 子：:=法亚- 如特開纖_233611號公報揭示之以從含有二氧化 夕以外之無機化合物之二氧化 徵之多孔質二氧化娜子之製造方法，=:= 二氧化_子表面用二;=:之二二化广氧化㈣ 以調製多孔質二氧化賴:=;:接者進行脫紹處理 (I)核粒子： =粒子可使用二氧切_氧化㈣二氧切微粒子等 該等以溶膠狀之分散液形態❹。該等溶膠 、、之刀政液可經由公知之製法獲得。例如將矽酸鹽之 切較與驗可社㈣鈉等無機化合物之水溶液 ;:::於阳值10以上之鹼水溶液中’必要時添加於分 =作為種粒子之si02_A1203(石夕與翻之複合氧化物）、邱 對庫si上之驗水溶液中而製得。上述種粒子之分散液為在 =s1〇2_Al2〇3等之金屬鹽、金屬鹽之混合物或金屬醇鹽 H口酸或驗，使該金屬鹽等進行水解，必要時加熱或邊 加熱邊使成長而獲得。 夕包覆層之形成： 八丑添加於二氧化矽_氧化鋁系二氧化矽微粒子之溶膠狀 =散液之二氧化砍包覆層用原料，以將梦之驗金屬鹽（水玻 肖）脫驗獲得之石夕酸液較佳。上述核粒子之分散溶劑單獨為 317388 22 ，1266752 » ! 水日守，或為水與有機化合物之混合物但相對於有機化合物 水之比率高時，可經由矽酸液進行包覆處理。用矽酸液進 行包覆處理時，在上述分散液中添加規定量之矽酸液，同 時加入鹼使矽酸聚合並使矽酸沉著於上述核粒子表面。矽 酸，添加量在核粒子為二氧化矽_氧化鋁系二氧化矽微粒 子時，為可進行後述經由添加酸之脫鋁處理範圍之量。 二氧化矽原料亦可使用水解性有機矽化合物。水解性 之有機矽化合物可使用以通式RnSi(〇R，）表 ♦锁但是，R、R，為烧基、芳基、乙稀基、丙稀基等:基基 :11為〇、1、2或3]，又以四甲氧基矽烷、四乙氧基矽烷、 ： 四異丙氧基矽燒等四烷氧基矽烷較佳。 添加方法可列舉將在該等烷氧基矽烷、純水及醇之混 合溶液中添加少量鹼或酸作為催化劑之溶液加入上述核粒 子分散液中，使烧氧基石夕烧水解生成之石夕酸沉著於該核粒 子表面之方法。此時，可將烷氧基矽烷，、催化劑同時 鲁添加於分散液中。鹼催化劑可使用氨、鹼金屬之氫氧化物、 胺類等。又，酸催化劑可使用各種無機酸及有機酸。 亦可將燒氧基石夕烧與上述石夕酸液併用進行包覆處理。 必要時可併用二氧化石夕源以外之無機化合物進行包覆處 理’亦可使用調製上述核粒子使用之驗可溶之無機化合 物。二氧化石夕原料及必要時添加之無機化合物之添加:， 2將核粒子包覆後在酸性溶劑t可溶之金屬可溶出範圍之 量較佳。包覆量少時，上述核粒子會溶解或崩解。包覆層 之厚度通常以lnm至1〇11111較適當。 317388 23 1 1266752 銘离王里_ 部構成包覆f之上述核粒子除去-部分或全 ιίΐ! 可製造作為外殼之包覆層内部具有 4狀微粒子。要除去—部分或全部構成核粒子 機酸將=:=核::編^ ’、 /或將上述核粒子分散液與陽離 乂換树脂接觸而將銘進行離子交換除去之方法。 ^去紹時核粒子分散液中核粒子之濃度依處理溫度而 /、，換鼻為氧化物以在（U至50重量％為宜，在〇 5至25 之範圍較佳。若未滿（U重量％，形成二氧化石夕包覆 、曰之一乳化矽可能會溶解，同時由於濃度低而處理效率 ϋ粒子之濃度若超過50重量％，則銘不易以少次數處 理而除去必要量。 &amp;除去㈣進行至經由除去！g而獲得之多孔f二氧化石夕 微粒子中八地之重量比率⑷办/⑷办+仙小㈣為 0.01至5重量％為止較佳。除去鋁之分散液可經由限外過 遽等公知之洗淨方法洗淨。x，必要時可將分散溶劑以有 機分散溶劑取代。分散於由此獲得之分散溶膠中之二氧化 石夕系微粒子，外殼由多孔f二氧切層構成，内部之空洞 3有洛劑及/或氣體。核粒子未完全除去時，多孔質之物 質會殘留在空洞内。 α)分散溶劑： 本發明使用之分散溶劑（b)可列舉水； τ醇、乙醇'異丙醇、正丁醇、甲基異甲醇等醇類； 317388 24 1266752 丙酮、2_丁酮、乙基戊基甲酮、二丙酮醇、異佛爾酮、 環己酮等酮類； N，N-二甲基甲醯胺、N，N_二甲基乙醯胺等醯胺類； 二乙醚、異丙醚、四氫呋喃、丨，4_二噁烷、3,4•二氳_2h_ 吡喃等醚類； 2-甲氧基乙醇、2-乙氧基乙醇、2-丁氧基乙醇、乙二 醉'一甲鍵專乙二醇趟類； 2-甲氧基乙基乙酸酯、2_乙氧基乙基乙酸酯、2_丁氧 鲁基乙基乙酸酯等乙二醇醚乙酸酯類，· 乙酸甲酯、乙酸乙酯、乙酸異丁酯、乙酸戊酯、乳酸 乙酯、碳酸伸乙酯等酯類； 苯、甲苯、二甲苯等芳族烴類； 己烷、庚烷、異-辛烷、環己烷等脂肪族烴類； 氣甲烧1’2 一氣乙院、一氣丙烧、氯苯等鹵化煙 類； φ 一甲亞楓等亞楓類； N-甲基_2』比咯烷酮、N•辛基吡咯烷酮等吡咯烷酮 類等。該等分散溶劑以與調製後述抗污被膜形成用組成物 或墨水接受層形成用塗佈液時之黏合劑之相溶性加以選 擇。 省等分散溶劑可單獨使用1種，亦可2種以上併用。 於本說明書，將上述分散溶劑（b)作為後述之墨水接受 層形成用塗佈液之原料使用時，該分散溶劑（b)亦稱為「由 水及/或有機溶劑組成之溶劑（b，）」。 317388 25 r1266752 以及二 ⑹及八：:二二氧化鈦微粒子與多孔質二氧切微粒子 二成之含有鈦之石夕溶膠(含有鈦之石夕溶 人=將二氧化鈦微粒子與多孔f二氧化石夕微 ί:= 分散溶劑中而製得，較佳將由上述 及上述分散㈣⑻組成之鈦轉與由上述 二二Γ化石夕微粒子及上述分散溶劑⑻組成之石夕溶膠 耽*合而製成。 明含有鈦之㈣膠之上述多孔質二氧化石夕微 石夕與上述二氧化鈦微粒子中之鈦之曹旦斗她々々 為Si〇2與丁i〇2之重量比時較佳為叫/ =、异 =:，更八佳為 Si〇2/Ti〇2，16,—^ 降低之\^有欽之石夕溶膠或後述之墨水接受層之透明性有 鈦之^膜I ^ ’ Sl〇2//Tl02若超過21，000，則將含有上述 以卜作為抗污塗膜形成用組成物之原料使用時，由於 =氧化鈦微粒子之光觸媒作用為基礎之抗污效果變 ;I '可垢刀解所需之時間有顯著增長之傾向。將上述含 ^ t轉料墨水接受層形成職佈液之純使用時， 弱，化欽微粒子之光觸媒作用為基礎之消色效果變 、p子或印圖消色所需之時間有顯著增長之傾向。 317388 26 f 1266752 ♦ r 於本發明使用之經鈦酸酯系化合物進 =多孔質二氧化石夕微粒子(a2)(以下亦稱為「：面：：：成 質二氧化㈣粒子（a2)」）’被認為係在多孔質二^ = 粒子之表面被例如具有下述式（句表示之構造之二^ :夕微 ;=膜包覆，該被膜發揮與二氧化鈦微；羊光太 化機能。 TU之先催 [化 11]The puller is in a uniform-dispersed state and is easily formed into a film. When the emulsified titanium U is used as the raw material of the titanium-containing sol, the surface charge amount is: t; the porous coating of the coating liquid for the formation of the above-mentioned ink-receiving layer is coated with the upper ink-receiving layer. If there is = Shixi sol or eq/g, it is divided into 4 ancient, direction, right over 150 / / g shell J knife placed with the above porous silica dioxide, there is a titanium sol, the viscosity of the sol has become higher ^ or The ink containing the sol as a main component has a high degree of titanium, and it is difficult to form a uniform film by the viscosity of the coating liquid for forming the core layer. If the surface charge amount is used in the dioxide dioxide, Then: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The ink was sufficiently dispersed in the substrate to receive the titanium ruthenium particles. As a result, a-deuterated ffl ^ * The substrate of the 5 accepted substrate with the ink receiving layer exhibited good decolorization in July. 21 1266752 The porous silica stone used in the present invention is particularly limited, and may be appropriately The method for producing porous dioxins which are derived from the dioxidation index of an inorganic compound other than the cerium oxide, as disclosed in the publication: ??? The subsurface is treated with two; =: the dichroic oxidation (4) to modulate the porous dioxide: ???;: the receiver is subjected to the removal treatment (I) nuclear particles: = particles can be used for dioxo-oxidation (tetra) dioxotomy The granules and the like are in the form of a sol-like dispersion. The sols and the kiln solution can be obtained by a known method, for example, by cutting a bismuth citrate with an aqueous solution of an inorganic compound such as sodium (C) sodium; :: In the aqueous alkali solution of 10 or more, if necessary, it is added to the fraction of the si02_A1203 (composite oxide of Shixi and Fu) and the aqueous solution of Qiu on the library. The dispersion liquid is obtained by hydrolyzing the metal salt or the like with a metal salt such as =s1〇2_Al2〇3 or a mixture of metal salts or a metal alkoxide H-port acid, and if necessary, heating or heating. The formation of the eve coating: eight ugly added to the cerium oxide _ alumina system diox The sol-form of the granules of the granules is a raw material for the oxidized chopping coating layer of the granules, and the sulphuric acid solution obtained by de-testing the metal salt of the dream (water glass porphyrin) is preferably used. The dispersing solvent of the above-mentioned nucleus particles is 317388. 22 ,1266752 » ! When the water is kept, or it is a mixture of water and organic compounds, but the ratio of water to organic compound is high, it can be coated with citric acid. When coated with citric acid, A predetermined amount of citric acid liquid is added to the dispersion, and a base is added to polymerize citric acid to deposit lanthanum on the surface of the core particles. The amount of citric acid added is when the core particles are cerium oxide-alumina-based cerium oxide microparticles. The amount of the dealumination treatment range by adding an acid described later can be performed. A hydrolyzable organic hydrazine compound can also be used as the ceria raw material. The hydrolyzable organic ruthenium compound can be used as the formula RnSi(〇R,), but the R, R, is an alkyl group, an aryl group, an ethylene group, an acryl group, etc.: a base group: 11 is 〇, 1 Further, a tetraalkoxy decane such as tetramethoxy decane, tetraethoxy decane or tetraisopropoxy oxime is preferred. The addition method may be a method in which a solution in which a small amount of a base or an acid is added as a catalyst in a mixed solution of the alkoxydecane, pure water and an alcohol is added to the above-mentioned core particle dispersion, and the alkoxylate is hydrolyzed by the alkoxylation. A method of immersing on the surface of the core particle. At this time, the alkoxydecane and the catalyst may be simultaneously added to the dispersion. As the base catalyst, ammonia, an alkali metal hydroxide, an amine or the like can be used. Further, various inorganic acids and organic acids can be used as the acid catalyst. Alternatively, the calcined oxygen stone can be used in combination with the above-mentioned australis acid solution for coating treatment. If necessary, the inorganic compound other than the source of the cerium oxide may be used in combination for coating treatment. The inorganic compound which is soluble in the preparation of the above-mentioned core particles may also be used. The addition of the raw material of the cerium oxide and the inorganic compound to be added if necessary: 2, the amount of the metal soluble in the acid solvent t after the core particles are coated is preferably in the range of elution. When the amount of coating is small, the core particles are dissolved or disintegrated. The thickness of the cladding layer is usually from 1 nm to 1 〇 11111. 317388 23 1 1266752 The core particles removed from the _ part of the composition _ part of the coating f - part or all ι ΐ 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可To remove - part or all of the constituents of the nuclear particle organic acid =: = nucleus:: </ br>, or a method in which the above-mentioned core particle dispersion is contacted with a cation-removing resin to carry out ion exchange removal. ^ The concentration of the core particles in the core particle dispersion is determined according to the treatment temperature, and the nose is changed to oxide (U to 50% by weight, preferably in the range of 5 to 25). When the weight is %, the formation of the oxidized cerium in the form of cerium dioxide may be dissolved, and the concentration of the cerium is less than 50% by weight due to the low concentration, and it is difficult to remove the necessary amount by a small number of treatments. It is preferable to remove (4) to the weight ratio of the eight places in the porous f-earth dioxide fine particles obtained by removing !g (4), (4), and the small (four) is preferably 0.01 to 5% by weight. The aluminum-dispersing liquid can be removed. It is washed by a known washing method such as limiting the amount of x. If necessary, the dispersing solvent may be replaced by an organic dispersing solvent, and the disulfide fine particles dispersed in the dispersed sol thus obtained may be made of porous fr The oxygen-cut layer is formed, and the internal cavity 3 has an agent and/or a gas. When the core particles are not completely removed, the porous substance remains in the cavity. α) Dispersing solvent: The dispersing solvent (b) used in the present invention is exemplified Water; tau alcohol, ethanol Alcohols such as alcohol, n-butanol and methyl isomethanol; 317388 24 1266752 ketones such as acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone, cyclohexanone; N, N - decylamines such as dimethylformamide and N,N-dimethylacetamide; diethyl ether, diisopropyl ether, tetrahydrofuran, hydrazine, 4_dioxane, 3,4•diindole-2h_pyran Ethers; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylidene-one-bonded ethylene glycol oxime; 2-methoxyethyl acetate, Glycol ether acetate such as 2_ethoxyethyl acetate, 2_butoxyglutide ethyl acetate, · methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, lactic acid Ester such as ethyl ester or ethyl carbonate; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, iso-octane and cyclohexane; gas-fired 1'2 gas B-type hospital, one-burning, chlorobenzene and other halogenated tobaccos; φ 甲甲亚枫 and other yafeng; N-methyl _2 』 pyrrolidone, N. octyl pyrrolidone and other pyrrolidone, etc. And a composition for forming an antifouling film to be described later And the compatibility of the binder in the case of the coating liquid for forming the ink-receiving layer is selected. The dispersing solvent may be used singly or in combination of two or more kinds. In the present specification, the dispersing solvent (b) is described later. When the raw material of the coating liquid for forming an ink receiving layer is used, the dispersion solvent (b) is also referred to as "a solvent (b,) composed of water and/or an organic solvent". 317388 25 r1266752 and two (6) and eight:: two Titanium dioxide microparticles and porous dioxygen microparticles are prepared by using a titanium-containing sol (containing titanium-titanium-dissolving person = titanium dioxide microparticles and porous f-earth dioxide: a dispersion solvent, preferably The titanium consisting of the above-mentioned and the above-mentioned dispersions (4) and (8) is produced by combining the above-mentioned diterpene fossil granules and the above-mentioned dispersion solvent (8). It is preferred that the above-mentioned porous silica dioxide containing titanium (tetra) gel and the titanium in the titanium dioxide microparticles are the weight ratio of Si〇2 to 丁i〇2. , ==,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, When 2//Tl02 exceeds 21,000, when the above-mentioned material is used as a raw material for forming an antifouling coating film, the antifouling effect based on the photocatalytic action of the titanium oxide fine particles is changed; There is a significant increase in the time required for the knife solution. When the above-mentioned t-substrate ink receiving layer is formed into a pure use liquid, the photochromic effect based on the photocatalytic action of the puncture microparticles is changed, and the time required for the p sub-print or the printing decolorization is significantly increased. tendency. 317388 26 f 1266752 ♦ r The titanate-based compound used in the present invention is a porous silica dioxide granule (a2) (hereinafter also referred to as ": face::: masogenic dioxide (four) particle (a2)" It is considered to be attached to the surface of the porous material. For example, the surface of the particle is represented by the following formula (the structure of the sentence is represented by the formula: the film is coated with the film; the film is coated with the titanium dioxide micro; the sheep light is too functioning. TU First reminder [11]

(4) 該欽酸酯化合物係使用具有含鈦原子之水解性基之化 合物’可列舉例如四料基鈦化合物、聽鈦化合物、欽 螯合物、鈦酸酉旨系偶合劑等。其中以下述通式⑴至⑺之任 一者表示之鈦酸酯系化合物較佳。 [此處，η為1至4之整數； R11為碳原子數1至6之烧氧基，η=2或3時2個r11 可結合形成下述通式（la)表示之環狀構造，亦可將結合於 通式（la)中鄰接氧原子之碳原子之_之2個氳原子以氧原 子取代，形成下述通式（lb)表示之環狀構造； R為碳原子數1至5之烴基或下述通式（lc)、（ld)、 317388 27 〇(4) The phthalate compound is a compound having a hydrolyzable group containing a titanium atom, and examples thereof include a tetrabasic titanium compound, a titanium compound, a chelate compound, and a barium titanate coupling agent. Among them, a titanate compound represented by any one of the following general formulae (1) to (7) is preferred. [wherein, η is an integer of 1 to 4; R11 is an alkoxy group having 1 to 6 carbon atoms, and when n = 2 or 3, two r11 may be bonded to form a cyclic structure represented by the following formula (la), Alternatively, two ruthenium atoms bonded to a carbon atom adjacent to an oxygen atom in the formula (la) may be substituted with an oxygen atom to form a cyclic structure represented by the following formula (lb); R is a carbon number of 1 to a hydrocarbon group of 5 or the following formula (lc), (ld), 317388 27 〇

0—CqH2q+1 1266752 (le)、（If)、（lg)或（lh)表示之有機基 [化 12] H2C— H2xCx—0〆 (其中，χ為1至7之整數，較佳為1 [化 13] o=c— • H2yCy- (其中，y為1至7之整數，較佳為1 [化 14] 〇0—CqH2q+1 1266752 (le), (If), (lg) or (lh) an organic group [12] H2C—H2xCx—0〆 (wherein χ is an integer of 1 to 7, preferably 1 o=c— • H2yCy- (where y is an integer from 1 to 7, preferably 1 [14] 〇

II '~0—C—CpH2p+1 拳（其中，P為4至3〇之整數，較佳為 [化 15] 2 (其中，q為4至30之整數，較佳為 (la) 至3之整數）， (lb) 至3之整數）， (lc) 5至20之整數）， ⑽ 5至20之整數）， 28 317388 1266752 [化 16] Ό- ΟII '~0—C—CpH2p+1 boxing (wherein P is an integer of 4 to 3 ,, preferably [Chem. 15] 2 (where q is an integer of 4 to 30, preferably (la) to 3 Integer), (lb) to an integer of 3), (lc) an integer from 5 to 20, (10) an integer from 5 to 20), 28 317388 1266752 [Chem. 16] Ό- Ο

〇C q ,H2q (le) 數） (其中，q，為4至3〇之整數，較佳為5至2〇 [化 17] ^〇C q , H2q (le) number) (where q is an integer of 4 to 3 ,, preferably 5 to 2 〇 [Chem. 17] ^

•OCrH2rNHCr，H2r,NH 2 (If) 之整數 籲（其中，r及r’分別為！以上之整數，r+r，為4至％ 較佳為4至20之整數）， [化 18] Ο II 〇—s- II 〇• An integer of OCRH2rNHCr, H2r, NH 2 (If) (where r and r' are each an integer of !, r+r, preferably 4 to %, preferably an integer of 4 to 20), [Chem. 18] II 〇-s- II 〇

Cshs+l (lg) (其中，S為1至30之整數，較佳為5至2〇之敕 [化 19] i 數），Cshs+l (lg) (wherein S is an integer from 1 to 30, preferably from 5 to 2 敕 [化19] i number),

Ct Ή2ί (lh) (其中’t及t’分別為丨至扣之整數，較佳為〗至3之敕數 R21TiR22R232 ...........⑺ 正 ， [此處’R21為碳原子數1至4之炫氧基，r22為下述通式（2a) 29 317388 1266752 表示之有機基，R23 Λ下、+、、孟 [化20] 為下述通式（2b)表示之有機基， 0 2u+1Ct Ή2ί (lh) (where 't and t' are the integers from 丨 to buckle, respectively, preferably 〗 to 3, R21TiR22R232 ...........(7) 正, [here 'R21 is a methoxy group having 1 to 4 carbon atoms, and r22 is an organic group represented by the following formula (2a) 29 317388 1266752, and R23 anthracene, +, and montene are represented by the following formula (2b). Organic base, 0 2u+1

〇—C——CUH (2a) (其中，u為4至30之整翁，私乂土达 車乂 ^土為5至2 0之敕金今、 [化21] 、正数）， O R，〇—C——CUH (2a) (where u is an integer of 4 to 30, private to Tuda 乂 ^ soil is 5 to 20 敕 Jin Jin, [Chem. 21], positive number), O R,

II I 2II I 2

Ό——C~C=CH (2b) (其中’ R’為3氫原子或碳原子數】至4之燒基几 R 4T1 · [p(〇c2wh2w+1)2(oh)]2 [式中，^為碳原子數1至20，較佳為2至··10之燒氧基， ^烧乳基中虱原子之—部分可經碳原子數為1至Η土， 鍵及雙鍵中之至少一者之有機基取代。 W為4至2G之整數，較佳為5至2()之敕 取气 上述妙之例可列舉嶋、乙氧基、： 丙氧基、正丁氧基、第三-丁氧基等。 内虱基異 上述R12之例可列舉p基、乙基、 第三-丁基、正丁基、正戍基等。 @基、異丙基、 &quot;上述之例可列料氧基、乙氧基、正丙氧基、異 丙氧基、正丁氧基、第三-丁氧基等。 之例可列舉甲氧基、乙氧基、正丙氧基、異 丙乳基、正丁氧基、第三·丁氧基、取代丙氧基、取代丁氧 317388 30 ' 1266752 基等。 該等鈦酸酯系化合物具體而言可列舉異丙基三異硬酯 酿基鈦酸酯、異丙基三（二辛基焦磷酸酯）鈦酸酯、異丙基 二（N-胺基乙基-胺基乙基）鈦酸醋、四（2,2-二烯丙氧基曱基 -1-丁基）雙（二十七烷基）磷酸酯鈦酸酯、雙（二辛基焦磷酸 酯）羥乙酸酯鈦酸酯、雙（二辛基焦磷酸酯）乙撐鈦酸酯、異 丙基二個十二烷基苯石黃酿基鈦酸g旨、四異丙氧基鈦酸醋等。 用上述鈦酸酯系化合物進行表面修飾前之多孔質二氧 鲁化矽微粒子經由BET法求得之比表面積在3〇〇m2/gu :上，較佳在350m2/g以上。比表面積若比3〇〇m2/g小， _ 則口包復多孔夤一氧化梦微粒子表面之鈦酸醋之量變少， ， 以該被膜之光活性為基礎之優越抗污效果或消色效果有不 易發揮之傾向。 用上述鈦酸g曰系化合物進行表面修飾前之多孔質二氧 化矽微粒子之平均粒徑為5至1〇〇nm，較佳1〇至9〇1。Ό——C~C=CH (2b) (where 'R' is 3 hydrogen atoms or carbon atoms】to 4 calcining bases R 4T1 · [p(〇c2wh2w+1)2(oh)]2 Wherein, ^ is an alkoxy group having 1 to 20 carbon atoms, preferably 2 to 10, and a part of a ruthenium atom in the calcined base may have a carbon number of 1 to alumina, a bond and a double bond. The organic group is substituted with at least one of them. W is an integer of 4 to 2G, preferably 5 to 2 (). The above-mentioned examples include hydrazine, ethoxy, propoxy, n-butoxy And a third-butoxy group. Examples of the above-mentioned R12 include a p group, an ethyl group, a tri-butyl group, a n-butyl group, a n-decyl group, etc. @基,isopropyl, &quot; Examples thereof include an oxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a tert-butoxy group, etc. Examples thereof include a methoxy group, an ethoxy group, and a n-propoxy group. Base, isopropylidene, n-butoxy, tert-butoxy, substituted propoxy, substituted butoxy 317388 30 ' 1266752, etc. The titanate compounds may specifically be isopropyl III Isostearyl silicate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl Bis(N-Aminoethyl-aminoethyl)titanate, tetrakis(2,2-diallyloxydecyl-1-butyl)bis(heptadecyl)phosphate titanate , bis(dioctyl pyrophosphate) glycolate titanate, bis(dioctyl pyrophosphate) ethylene titanate, isopropyl two dodecyl benzoate yellow titanate Or a tetraisopropoxy titanate or the like. The specific surface area of the porous dioxonium hydride fine particles obtained by surface modification with the above titanate compound is 3 〇〇m 2 /gu : Preferably, it is more than 350 m 2 /g. If the specific surface area is smaller than 3 〇〇 m 2 /g, the amount of titanic acid on the surface of the porous granules is reduced, and based on the photoactivity of the film. The superior antifouling effect or the decolorizing effect tends to be difficult to exert. The average particle diameter of the porous ceria particles before surface modification using the above titanate g-based compound is 5 to 1 〇〇 nm, preferably 1 〇 to 9〇1.

平均粒徑若比該範圍小，則溶膠之分散安定性變低，與黏 合劑等混合時會發生障礙。 一平均粒徑若比該範圍大，則將上述含有鈦之溶膠作 抗3塗膜形錢組成物之原料使㈣，由於使用含有欽 抗污被膜之透明性降低，在具有該抗污被膜 二基：：面曾產生顏色暗淡等外觀惡化或光催化機能不能 佈:::料:η欽之溶膠作為墨水接受層形成用塗 接受層之透明性:低，：:吏：含有鈦之石夕溶膠形成之墨水 -在形成墨水接受層之印刷用基材表 317388 31 1266752 面冒產生顏色暗淡等外觀惡化或消色機能不能充分發揮。 用上述欽酸酯系化合物進行表面修飾前之多孔質二氧 =| u粒子之表面電荷量以丨〇至15〇 v叫/g較佳。表面 私何1若末滿10// eq/g，則溶膠之分散性有不安定之傾 =表面電荷1若超過150// eq/g，則溶膠之黏性變高， ^有忒夕孔貝一氧化矽微粒子作為主成分之後述抗污被膜 也，用組成物之黏度亦變高，不易形成均一之被膜。或以 夕孔貝—氧化石夕微粒子作為主成分之墨水接受層形成用 主抹液之黏度亦變高，不易形成均一之接受層。 上述表面修飾多孔質二氧化矽微粒子中含有之矽 太之重里比，換异為81〇2與1102之重量比時較佳為Si02 1〇2=5 至 21，_，更佳為 Si〇2/Ti〇2=100 至 16，_。 =/加2未滿5時，含有鈦之㈣膠之透明性有降低之 傾向。 —方面Sl〇2/Tl〇2若超過21,000，則將上述含有 ，以之溶膠作為抗污塗膜形成用組成物之原料使用時，由於 ^被膜之光觸媒作用為基礎之抗污 將㈣分解所需之時間有顯著增長之 之溶膠作為墨水接受声报忐田^ 竹上疋3有欽 以，、… 接又層形成用塗抹液之原料使用時，由於 二;r:鈦微粒子之光觸媒作用為基礎之消色效果變 ΐ由色所需之時間有顯著增長之傾向。 s有敌容膠之，诰 由本發明之表面修飾多孔質二氧化石夕微粒子㈣及分 317388 32 1 1266752 ., 散溶劑（b)組成之含有鈦之矽溶膠（含有鈦之矽溶膠（a2s)) 較佳由將上述多孔質二氧化矽微粒子與水或由水及有機系 分散溶劑組成之矽溶膠用高速攪拌機邊攪拌邊於15。〇以〃 上’在10分鐘至2小時添加鈦酸酯化合物獲得。若 則鈦酸酯系化合物會水解、凝集。 ^ ^多孔質二氧化矽微粒子與鈦酸酯系化合物之配合比率 換算為Si〇2與Ti〇2之重量比，較佳為Si〇2//Ti〇2=5至 21，000,更佳為以〇2/^〇2 = 1〇〇至 i6 〇〇〇QSi〇2/Ti〇2 未 馨滿5時，含有鈦之石夕溶膠之透明性有降低之傾向。另一方 :面，Si〇2//Ti〇2若超過21,_，由於以二氧化欽系被膜之 :光觸媒作用為基礎之污染物質分解效果，亦即抗污效果降 低，將污垢分解所需之時間有顯著增長之傾向。 該等表面修飾多孔質二氧切微粒子（a2)光觸媒 優越，在形成含有該微粒子之抗污被膜之基材表面即使附 者有機化合物之污垢，經由紫外線照射可將污垢分解，更 •可經由與酸性氣體、臭氧等接觸將污垢分解。 該等表面修飾多孔質二氧化矽微粒 用為基礎之消色作用優越，在形成含有該微粒子之^作接 j之印刷用基材表面即使印字或印圖，該印字或印圖經 消^外線照射可消色’經由與酸性氣體、臭氧等接觸亦可 之矽溶塍&gt; 多孔之含有欽之石夕溶膠由上述之二氧化鈦微粒子與 貝一氧化矽微粒子（al)或上述表面修飾多孔質二氧化 317388 33When the average particle diameter is smaller than this range, the dispersion stability of the sol is lowered, and when it is mixed with a binder or the like, an obstacle occurs. When the average particle diameter is larger than the range, the titanium-containing sol is used as a raw material of the anti-three-coating film-forming composition, and (4), since the transparency of the film containing the anti-staining film is lowered, the anti-fouling film is provided. Base:: The surface has been dimmed and the appearance is deteriorated or the photocatalytic function is not able to be clothed:::Material: η 钦 sol is used as the ink receiving layer to form the coating layer. Transparency: Low, :: 吏: Contains titanium stone Ink formed by the sol-form-printing substrate table 317388 31 1266752 in which the ink receiving layer is formed is deteriorated in appearance such as dull color or the color erasing function is not sufficiently exhibited. The surface charge amount of the porous dioxane =| u particles before surface modification with the above-mentioned octanoate-based compound is preferably 丨〇 to 15 〇 v/g. If the surface is more than 10//eq/g, the dispersibility of the sol is unstable. If the surface charge 1 exceeds 150//eq/g, the viscosity of the sol becomes high. As the main component, the anti-fouling film described later is also used as the main component, and the viscosity of the composition is also high, so that it is difficult to form a uniform film. Or the ink repellency of the main smear formed by the ink-receiving layer forming the main component of the smectite-oxidized stone granules is also high, and it is difficult to form a uniform receiving layer. The surface-modified porous cerium oxide microparticles have a weight ratio of 矽 too, and the weight ratio of 81 〇 2 to 1102 is preferably SiO 2 1 〇 2 = 5 to 21, _, more preferably Si 〇 2 /Ti〇2=100 to 16, _. = / When 2 is less than 5, the transparency of the (4) rubber containing titanium tends to decrease. In the case where the above-mentioned sol is used as a raw material for the composition for forming an antifouling coating film, the anti-fouling based on the photocatalytic action of the film is (4). The sol that has a significant increase in the time required to be used as an ink to receive the sound of the 忐田^ 竹上疋3 has the intention to use, when the layer is formed with the raw material of the application liquid, because of the second; r: the photocatalytic effect of the titanium microparticles is The basic achromatic effect becomes a tendency for the time required for color to increase significantly. s has a gelatinous gel, a surface-modified porous silica dioxide granule (4) of the present invention and a fraction of 317388 32 1 1266752., a solvent containing titanium (b) containing a titanium sol (a titanium-containing sol (a2s) Preferably, the porous cerium oxide fine particles and water or a cerium sol composed of water and an organic dispersion solvent are stirred at 15 with a high speed mixer. It is obtained by adding a titanate compound at 10 minutes to 2 hours. If the titanate compound is hydrolyzed and aggregated. ^ ^ The ratio of the ratio of the porous cerium oxide microparticles to the titanate-based compound is converted to the weight ratio of Si 〇 2 to Ti 〇 2, preferably Si 〇 2 / / Ti 〇 2 = 5 to 21,000, more preferably When 〇2/^〇2 = 1〇〇 to i6 〇〇〇QSi〇2/Ti〇2 is not saturated 5, the transparency of the Titanium sol containing titanium tends to decrease. On the other hand, if the surface of Si〇2//Ti〇2 exceeds 21, _, the decomposition effect of the pollutants based on the photocatalytic action of the oxidized capsule is reduced, that is, the antifouling effect is lowered, and the dirt is required to be decomposed. There is a tendency for significant growth in time. The surface-modified porous oxidized microparticles (a2) are excellent in photocatalyst, and even if the surface of the substrate on which the anti-fouling film containing the microparticles is formed, even if the organic compound is contaminated, the dirt can be decomposed by ultraviolet irradiation, and more Contact with acid gas, ozone, etc. decomposes the dirt. The surface-modified porous cerium oxide microparticles have excellent decolorizing effect, and even if printing or printing is performed on the surface of the printing substrate containing the microparticles, the printing or printing is eliminated. Irradiation can be achromatic, and it can be dissolved by contact with an acid gas or ozone. The porous cerium sol consists of the above-mentioned titanium dioxide microparticles and beryllium oxychloride microparticles (al) or the above surface-modified porous granules. Oxidation 317388 33

I 1266752 矽U粒子（a2)及上述分散溶劑（b)組成，可作為配合於後述 抗/亏被膜形成用組成物或墨水接受層形成用塗抹液之含有 鈦之矽溶膠使用。 本發明之含有鈦之矽溶膠中矽與鈦之重量比換算為 Si〇2與Ti02重量比，較佳為Si〇2/Ti〇2=5至21，〇〇〇，更 佳為 SiO2/TiO2=100 至 16,000。Si〇2/Ti〇2 未滿 5 時，含 有鈦之矽溶膠之透明性有降低之傾向。另一方面，si〇2/ Τι〇2右超過21，〇〇〇，由於以上述二氧化鈦系被膜之光觸媒 作用為基礎之抗污效果變弱，將污垢分解所需之時間有顯 著增長之傾向。 ,必要日守可將由上述二氧化鈦微粒子與多孔質二氧化矽 U粒子（a 1)及上述分散溶劑（b)組成之含有鈦之矽溶膠（&amp;工s) 與由上述表面修飾多孔質二氧化矽微粒子（a2)及上述分散 溶劑（b)組成之含有鈦之矽溶膠（a2s)混合使用。 本發明之含有鈦之矽溶膠之固體成分濃度通常為丨至 # 30重量％，但不僅限於該範圍，以與後述之黏合劑成分混 合或以調製後述抗污被膜或墨水接受層之膜厚為目的，加 以適當調整較理想。 本發明之含有鈦之矽溶膠在不損壞本發明目的之範圍 内’根據所期望’更可含有防腐劑、防黴劑、抗菌劑、著 色料、褪色防止劑、分散劑、界面活性劑。 以下，對於使用本發明含有鈦之石夕溶膠之抗污被膜形 成用組成物、抗污塗膜、墨水接受層形成用塗抹液及附有 墨水接受層記錄用基材及該等之製造方法、記錄用基材之 317388 34 1266752 » k 再生方法加以說明。 L抗污被膜形成用組成物1 使用本發明之含有鈦之矽溶膠，可製造由該含有鈦之 矽溶膠與黏合劑（C)組成之抗污被膜形成用組成物。 上述黏合劑（C)可使用有機樹脂、纖維素類、澱粉或無 祛化合物。上述有機樹脂列舉苯乙烯·馬來酸酐共聚物、 苯乙烯·丙烯酸烷基酯共聚物、聚乙烯醇、含有矽烷醇之 乙烯·乙烯醇共聚物、聚乙烯吡咯烷酮、乙烯·乙酸乙烯 聚物、甲基乙基纖維素、聚丙烯酸鈉、聚乙晞聚胺、 聚酯、聚丙烯基醯胺、乙烯基吡咯烷 物:_子改性聚胺基甲酸酯樹脂、含第3級氮=二 系樹Μ答照曰本專利特開昭62-148292號公報）等；上述 纖維素類列舉生物纖維素等；上述無機化合物列舉石夕酸 ，石夕I鉀、;^酸敛等或該等之混合物、有機梦之水解物、 !有機改性之無機化合物、陶瓷等。 •，有上述鈦之石夕溶膠與上述黏合劑⑷以固體成分重 s 、3有鈦之石夕洛膠：黏合劑⑷至: $至6〇(但 j兩者之合汁作為100)之範圍混合較佳。 且成物必要時除了本發明之含有欽之 粒子、氧微粒子、二氧化發系微 鈦、氧化辞、滑石粉石反_、黏土、氧化 面活性劑、抗菌劑等。 ^ LM污被膜1 317388 35 ，1266752 . 層乾ί基上述抗污被膜形成用組成物形成層後將該 成in污被膜。在基材上塗抹上述抗污被膜形 對岸M 被㈣’塗抹方法並無特別之限制， =基材之種類採用適當之塗抹方法。具體而言可採用喷 覆法簾ί塗抹法、浸塗法、輕塗法、到板塗覆法、棒塗 等以往公知之方法。 為方法可採用風乾 各二Γ膜可在廣範圍之基材上形成，基材列舉由 2種主㈣成之附有塗膜之基板、金屬、 :二裝料紙或合成紙等紙、㈣片、樹脂薄膜 屬泊玻璃或该等之複合體等。 。 用途用組成物之塗抹量只要對應基材或 時，二ΐ二:= 材/為㈣用紙或0Η&quot; /m2。里通韦為1至5〇g/m2，較佳為2至30g 使用上述抗污被膜防止基材 膜附著有機化合物之污垢物質，發 可由將該抗污被膜用紫外線等光線照 氧接觸將污垢物質分解、除去達成。 或六、 列兴==二照射紫外線較佳。紫外線照射時之光源 牛、’又、且盃屬鹵素燈、鎵燈、水銀氙燈、閃光严等。 :由:::::亦::果。紫外線等晴置對應丄 積…射線里4，只要選擇掃描型、非掃描型之任何一種 317388 36 1266752 即可’照射條件只要對應將污垢分解必要之 照射寬度等即可。又，接觸 疋 〇02氣體等。 uum料s〇2氣體、 如在影㈣紙等紙類或⑽片之表 几3被膜時，可蔣μ … 取上 之墨水接為岸#用、被膜作為喷墨印刷等印刷時 外；:::：此時’附著於紙等之污垢物質經由紫 刷用墨水之種類，在# ^ 觸 分解，根據印 . 、在#土、水接文層中印字、印圖所踢收夕里 水經由紫外線照射或與 ^ =回：亦有貢獻。經由調整印刷用墨水之種 : 4、與酸性氣體或臭氧接觸之各條件 、“ ^ 之著色變淡。 使Ρ子、印圖 上述抗污被膜若適用於船底等， 卜 綠草等_箪咮&amp; _ 、《寸著於船底等之 早：、，“生物不需採取特別之方法即可抑制。 由本發明（a 1)平均粒徑為2至5 . 一尸 _子、平均粒徑為5 5 ln 之一氧化鈦微粒 &gt; T ”立枉為5至I00nm，經由 在3〇〇々g以上之多^^ ^件之比表面積 組成之含有鈦之石夕溶膠（als)形/、、亏、子:分散溶劑⑻ 在^ Γ 貝—減夕微粒子乾燥後之填充¥古， 在夕孔貝二氧化矽微粒子可配合更斤 ⑷又冋 適用作為抗污被膜時可發揮優越之抗污=化鈦微粒子， 在以由本發明（a2)平均粒徑為5 法求得之比表面積在綱m Vg以上1 G =，經由腿 粒子表面用鈦酸㈣化合物進行表面修飾之^化二= 317388 37 1266752 夕被=與⑻錄溶劑組成為特徵之含有鈦之石夕溶膠 =隹由於從夕孔質二氧切微粒子之多孔到中心部空洞 酸：處理’將多孔質二氧化卿子進行表面 越之抗污效果。 帛㈣“ _時可發揮更優 LI Μ ^ΙΑΜΛΜΜΛΛ^^_^2 本發明之墨水接受層形成用塗抹液含有上述本發明之 含有鈦之溶膠及黏合劑（c，）。 籲財說明書’墨水接受層形成用塗抹液所含之上述分 散溶劑⑻亦稱為「由水及Α戈有機溶劑組成之溶劑⑻」。 本發明之墨水接受層形成用塗抹液較佳含有 上述微粒子（a)[亦即二氧化鈦微粒子及多孔質二氧化 石夕微粒子（al)或用鈦酸酉旨系化合物進行表面修飾所成之多 孔質二氧化矽微粒子（a2)]l〇〇重量分及上述黏合劑（c，）5至 7重量分， • 上述分散溶劑（b)[由水及/或有機溶劑組成之溶劑（B)] 之重畺（WB)、上述微粒子⑷及上述黏合劑（c，）[⑷與（〇，）人 併稱為「固體成分」）之合計重量（Wa+Wc，）比為Wb : (WA+WC’)=99.9 至 50 : 〇.1 至 50[但是，合計為 1〇〇]。 構成上述微粒子（a)[亦即上述微粒子（al)或上述微粒 子(a2)]之矽及鈦之含量換算為si〇2/Ti〇2重量比在$至 21，000之範圍。 (c’）黏合劑 本發明墨水接受層形成用塗抹液使用之黏合劑（c，）可 317388 38 ^ 1266752 . 使用聚乙稀醇、改性聚乙稀醇、聚乙糧烷酮、改性聚 乙烯ΰ比嘻烧鋼等親水性聚合物。 站口 ^ (C )之使用夏依黏合劑之種類而異，以對於上 ，微粒子⑷[亦即上述微粒子（al)或上述微粒子㈣卿重 里刀為5至7重置分者較佳。又，必要時併用上述微粒子 (al)或上述微粒子（a2)時，對於其合計重量1〇〇重量，黏合 )之$以5 7重1分較理想。黏合劑（e，)之量若未滿 5重量分，則墨水接受層與片等基材之黏附力不足，墨水 ，又層谷易剝離’墨水接受層之強度不充分，^超過7重 罝分，則墨水接受量降低，耐水性降低。 本發明之墨水接受㈣成用塗抹液以提昇墨水接受層 與片等基材之純性，提昇墨水接受層之強度、耐氣候性， 調節墨水接受層之細孔構造為目的，亦可含有抗氧化劑、 纖維素類等有機聚合物、生物纖維、無機聚合物、無機微 粒子等。 • 里塗抹液之告方法、 含有二氧化鈦微粒子及多孔質二氧化矽微粒子 (al)[微粒子（ai)]之墨水接受層形成用塗抹液之製造方法 亚無特別之限制，可由將上述微粒子（al)、黏合劑（c，）及由 水及/或有機溶劑組成之溶劑（B)混合、製造，從實用之觀 點而言，以由將上述微粒子（al)分散於分散溶劑（b)所成之 含有鈦之矽溶膠（als)、上述黏合劑（c，）及由上述之水及/ 或有=溶劑所成之溶劑（B)混合、製造之方法較佳。 含有表面經以鈦酸酯系化合物進行表面修飾所成之多 317388 39 1266752 . 孔貝-氧化石夕微粒子（a2)[微粒子（a2)]之墨水接受層形成 用塗抹液之製造方法並無特別之限制，可由將上述微粒子 (^)、黏合劑⑹及由水及a戈有機溶劑組成之溶劑（B)混 :、製造、’從實狀觀點而言，以由將上述微粒子⑽分 月，了刀政 &gt;谷劑〇5)所成之含有鈦之石夕溶膠㈣、上述黏合劑 、c及由上述之水及/或有機溶劑所成之溶劑⑻混合、製 造之方法較佳。 ^了確保作為墨水接受層形成用塗抹液之流動性，於 鈦之石夕溶膠（als)或含有上述鈦之石夕溶膠中 量之上述分散溶劑⑻時，不需再次加入由水及/ 或有機〉谷劑所成之溶劑（B)。 上述各成分之混合操作通常使用 器、滾筒式分散機、3支_機、強力授掉器 混砂機等裝置。 超曰波 記錄用甚纣2 以由片狀基材（以下「基材基材 之墨水接受層組成 ）纟5亥基材表面形成 附有w水接雙層記錄用片較佳。 脂”膜並無特別之限制’使用Ρ£τ、氣化烯等樹 二:用：、普通紙、各種紙、鋼板、布等。該等基材可 預无用基劑(叩崎)處理後使用。 上述之二氧化鈦微粒子及 或上述表面修飾多 乳切微粒子⑻ 貝一虱化矽微粒子（a2)可為一次粒 317388 40 1266752 次粒子，更可將一次粒子與二次粒子混合。 ;:二 =二粒子在塗抹液中不易單分散為-次粒 子之=集之粒子。又，一次粒子中可含 開，一次粒子化者。 人T 丁胖 上述基材上形成墨水接受層之方法可 法’只要採用對應基材之種類為理想之方法即二。 附有墨水接受層記錄用基材具體而言可由將 接受層形成用塗抹液以嗔霧法、_ κ 涂覆法、《&quot;η 刮板塗覆法、棒 塗後，去i塗覆法寻塗抹於基材表面後乾燥形成。 又’附有墨水接受層記錄用基材可 或ΐ=Τ2)分散於水及〜機溶劑所成之= 成：塗抹液塗抹於基材表面，乾燥 合金屬化合物載擔於上述微粒子(鲁述微粒子⑽表 面形成。例如，必糾將添加驗之陽離子性水合全屬化入 物之溶液时霧法、缝法、到板塗覆法、棒塗覆法、^ 塗覆法等塗抹於片等基材上後經由乾燥’將陽離子性水人 金屬化合物擔载於上述微粒子（al)或上述微粒子㈣表面口。 該陽離子性水合金屬化合物列舉例如A12(0H) C1 :了擔載量以陽離子性水合金屬化合物與氧化物粒 子之重量比(陽離子性水合金屬化合物上述微粒子⑻ 或上述微粒子⑻)))在請5至0.2之範圍者較佳。此時， 陽離子性水合金屬化合物與（上述微粒子（al)或上述微粒 之比只要成為在上述範圍之濃度即可，陽離子性水 5金屬化合物溶液之濃度並無特別之限制。 317388 41 1266752 塗抹及乾燥可反覆進行。 由此形成之墨水接受層一般即使使用染料系墨水或顏 料系墨水之任何一種時，至少以具有細孔徑在3·4至 2,000nm範圍之細孔較佳。該細孔中以細孔徑為3·4至 30nm之細孔之細孔容積在〇·2至3〇ml/g之範圍或細孔 徑為30至2,0〇〇nm之細孔之細孔容積在〇·ΐ至2.5ml//g 之範圍較佳。 細孔徑為3.4至30nm之細孔之細孔容積若未滿〇2ml /g，則墨水之吸收容量小，會滲出，不能獲得鮮明且為高 精密度之圖像。又，細孔徑為3·4至3〇nm之細孔之細孔 容積若比3.0ml/g大，則染料之固定性降低，墨水接受層 之強度變低。 又曰 細孔徑為30至2,0〇〇nm之細孔之細孔容積若未滿 2.5ml/g，則顏料系墨水不能充分吸收，顏料粒子會殘存 於接受層表面，經由磨耗而剝離，附有墨水接受層記錄用 •，材會掉色。細孔徑為3〇至2,〇〇〇nm之細孔之細9孔容積 右大於2.5ml/g，則顏料粒子之固定性降低，印字後顏料 粒子大多會屯積在墨水接受層之下部（基材表面附近），在 附有墨水接受層記錄用基材描緣之文字或圖像會缺乏鮮明 在基材上形成之墨水接受層之厚度依基材之厚度、 刷物之用途、印刷用墨水之種類可任意設定，通常以在&quot; 至1〇〇/^之_較理想。墨水接受層之厚度若未滿〇 5· 則墨水之吸收容量不足而產生渗出，又，墨水使用 317388 42 1266752 j少時’色彩會降低。厚度比100/2 m厚之墨水接受層， =k抹不易獲彳寸，需進行複數次之塗抹，造成經濟性之 問題’在塗抹、乾燥時會產生裂紋、剝離。消色性亦變差。 上述墨水接受層每單位重量之細孔容積為經由如下所 述之水銀壓入法測定之值： ⑴將預先尋求片與墨水接受層重量比之附有墨水接受層 、彔用片’力0.2至〇.3g插入測定單元（〇 5cc容積），使用 QUANTA CHROME 公司製造之 aut〇SCAN 6〇 porpsimeter，水銀接觸角為l3G。，水銀表面張力為 473dy:/m2’將測定範圍設定於「高壓」，測定細孔分布。 ()接著攸測疋之細孔分布尋求細孔徑為3 4至3〇nm之 ^孔之細孔容積及細孔徑為3G至2,0(K)nm之細孔之細孔 谷積’從測定之記錄用片中接受層之重量尋求接I 1266752 The composition of the U particles (a2) and the dispersion solvent (b) can be used as a titanium-containing cerium sol which is incorporated in an anti-defective film-forming composition or an ink-receiving layer-forming coating liquid which will be described later. The weight ratio of cerium to titanium in the titanium-containing cerium sol of the present invention is converted to a weight ratio of Si 〇 2 to TiO 2 , preferably Si 〇 2 / Ti 〇 2 = 5 to 21, 〇〇〇, more preferably SiO 2 / TiO 2 =100 to 16,000. When Si〇2/Ti〇2 is less than 5, the transparency of the sol containing titanium tends to decrease. On the other hand, si〇2/ Τι〇2 is more than 21 right, and the antifouling effect based on the photocatalytic action of the above titanium dioxide-based film is weakened, and the time required for decomposing the dirt tends to increase remarkably. The titanium-containing cerium sol (&amp;s) composed of the above-mentioned titanium dioxide fine particles and the porous cerium oxide U particles (a1) and the above-mentioned dispersion solvent (b) and the surface-modified porous oxidizing agent A titanium-containing cerium sol (a2s) composed of cerium fine particles (a2) and the above-mentioned dispersion solvent (b) is used in combination. The solid content concentration of the titanium-containing cerium sol of the present invention is usually from 丨 to 30% by weight, but is not limited to this range, and is mixed with a binder component to be described later or to prepare a film thickness of the anti-fouling film or the ink-receiving layer described later. The purpose is to make appropriate adjustments. The titanium-containing cerium sol of the present invention may further contain a preservative, an antifungal agent, an antibacterial agent, a coloring agent, a fading preventing agent, a dispersing agent, and a surfactant, as long as it does not impair the object of the present invention. In the following, the anti-fouling film-forming composition, the anti-fouling coating film, the ink-receiving layer-forming applicator, and the ink-receiving layer-recording substrate, and the method for producing the same, The recording substrate 317388 34 1266752 » k regeneration method is described. L anti-fouling film-forming composition 1 Using the titanium-containing cerium sol of the present invention, a composition for forming an anti-stain film comprising the titanium-containing cerium sol and the binder (C) can be produced. As the above binder (C), an organic resin, a cellulose, a starch or an antimony compound can be used. The above organic resin is exemplified by a styrene·maleic anhydride copolymer, a styrene·alkyl acrylate copolymer, a polyvinyl alcohol, an ethylene/vinyl alcohol copolymer containing a stanol, a polyvinylpyrrolidone, an ethylene vinyl acetate polymer, and a Base ethyl cellulose, sodium polyacrylate, polyethyl amide polyamine, polyester, polypropylene decylamine, vinyl pyrrolidine: _ sub-modified polyurethane resin, containing grade 3 nitrogen = two The above-mentioned cellulose is exemplified by biocellulose, and the inorganic compound is exemplified by liningoic acid, shixi I potassium, acid concentrating or the like. Mixtures, organic dream hydrolysates, organically modified inorganic compounds, ceramics, and the like. • There is a titanium sol with the above-mentioned binder (4) with a solid component weight s, 3 with a titanium stone: a binder (4) to: $ to 6 〇 (but the combination of the two as 100) Range mixing is preferred. Further, in addition to the present invention, in addition to the particles of the present invention, oxygen microparticles, oxidized hair microtitanium, oxidized words, talc powder, clay, oxidizing surfactant, antibacterial agent and the like. ^ LM fouling film 1 317388 35 ,1266752 . The layer is formed into a layer by the composition for forming an antifouling film, and then the film is formed. Applying the above-mentioned anti-fouling film to the substrate is not particularly limited by the (four)' application method, and the type of the substrate is appropriately applied. Specifically, a conventionally known method such as a spray coating method, a dip coating method, a light coating method, a sheet coating method, or a bar coating method can be employed. In the method, the air-drying film can be formed on a wide range of substrates, and the substrate is exemplified by two kinds of main (four) substrates with a coating film, metal, two-load paper or synthetic paper, and (four) sheets. The resin film is a beryl glass or a composite of the above. . The amount of the composition used for the application is as long as it corresponds to the substrate or time, the second: = material / (four) paper or 0 Η &quot; / m2. Ritutonvir is 1 to 5 〇g/m2, preferably 2 to 30 g. The above-mentioned anti-fouling film is used to prevent the substrate film from adhering to the fouling substance of the organic compound, and the anti-fouling film may be irradiated with ultraviolet rays or the like to irradiate the dirt. Material decomposition and removal are achieved. Or six, Lehing == two irradiation of ultraviolet light is preferred. The light source when the ultraviolet light is irradiated, the cow, the 'and the cup is a halogen lamp, a gallium lamp, a mercury lamp, a flashing light, and the like. : by::::: also:: fruit. In the ray, the ray is equal to any one of the scanning type and the non-scanning type. 317388 36 1266752 can be used as long as the irradiation condition is necessary to decompose the dirt. In addition, it is in contact with 疋 〇 02 gas. Uum material s〇2 gas, such as paper (4) paper or (10) sheet of the film 3, can be taken from the water to the shore #, the film as inkjet printing, etc.; ::: At this time, the dirt that adheres to the paper, etc., is decomposed by the type of ink used in the purple brush, and is printed according to the print, the print on the #土, the water layer, and the print. UV irradiation or with ^ = back: also contributes. By adjusting the type of printing ink: 4. The conditions for contact with acid gas or ozone, "^ The color of the color becomes lighter. If the anti-fouling film of the tweezers and the printed image is applied to the bottom of the ship, etc., & _, "In the early days of the ship, etc.:," "Biology does not need to take special measures to suppress. From the present invention (a1), the average particle diameter is 2 to 5. One corpse, the average particle diameter is 5 5 ln, one of the titanium oxide fine particles &gt; T 枉 枉 is 5 to 100 nm, and is above 3 〇〇々g The specific surface area of the ^^^ component consists of titanium-containing sol-like sol (als), and the loss of the sub-dispersion solvent (8) in the ^ Γ — - 减 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 , , , , , The cerium oxide microparticles can be used in combination with more smear (4) and can be used as an anti-fouling film to provide superior anti-fouling = titanium granules, and the specific surface area obtained by the method (a2) having an average particle diameter of 5 is in the range of m Vg. Above 1 G =, surface modification by surface modification of the surface of the leg particles with a titanic acid (tetra) compound = 317388 37 1266752 被 = = (8) The composition of the solvent is characterized by the inclusion of titanium sol sol = 隹 due to the uranium The porosity of the oxygen-cut microparticles to the center of the cavity acid: treatment 'to make the porous dioxide dioxide surface to the anti-fouling effect. 帛 (4) " _ can play a better LI Μ ^ ΙΑΜΛΜΜΛΛ ^ ^ _ ^ 2 ink of the invention The coating liquid for receiving layer formation contains the above-mentioned titanium-containing sol and binder of the present invention c,). The dispersing solvent (8) contained in the application liquid for forming the ink receiving layer is also referred to as "solvent (8) composed of water and organic solvent." The application liquid for forming an ink receiving layer of the present invention preferably contains the above fine particles (a) [that is, titanium dioxide fine particles and porous silica fine particles (al) or a porous surface formed by a surface modification of a barium titanate-based compound. The cerium oxide microparticles (a2)] l 〇〇 〇〇 重量 and the above binder (c,) 5 to 7 parts by weight, • the above dispersion solvent (b) [solvent composed of water and/or organic solvent (B)] The total weight (Wa+Wc,) ratio of the weight (WB), the above-mentioned fine particles (4), and the above-mentioned binder (c,) [(4) and (〇,) people are referred to as "solid components") is Wb: (WA+WC) ')=99.9 to 50: 〇.1 to 50 [however, the total is 1〇〇]. The content of ruthenium and titanium constituting the fine particles (a) (i.e., the above fine particles (al) or the fine particles (a2)) is converted into a weight ratio of si 〇 2 / Ti 〇 2 in the range of $ to 21,000. (c') Adhesive The adhesive (c,) used in the application liquid for forming an ink receiving layer of the present invention can be used as 317388 38 ^ 1266752. Using polyethylene glycol, modified polyethylene glycol, polyacetone, modified Polyethylene ruthenium is a hydrophilic polymer such as bismuth-fired steel. The station mouth ^ (C) varies depending on the type of Xia Yi binder, and it is preferable to reset the score for the upper, fine particles (4) [that is, the above-mentioned fine particles (al) or the above-mentioned fine particles (four). Further, when the above-mentioned fine particles (al) or the above fine particles (a2) are used in combination, it is preferable to use a weight of 1 〇〇 for a total weight of 1 。 and a weight of 5 7 for 1 minute. If the amount of the adhesive (e,) is less than 5 parts by weight, the adhesion between the ink receiving layer and the substrate is insufficient, and the ink is easily peeled off. The strength of the ink receiving layer is insufficient. In this case, the ink receiving amount is lowered and the water resistance is lowered. The ink of the present invention receives (4) the application liquid to enhance the purity of the substrate such as the ink receiving layer and the sheet, enhance the strength of the ink receiving layer, weather resistance, and adjust the pore structure of the ink receiving layer, and may also contain anti- Organic polymers such as oxidizing agents and celluloses, biofibers, inorganic polymers, inorganic fine particles, and the like. • The method for injecting the liquid, the method for producing the ink-receiving layer-forming coating liquid containing the titanium dioxide fine particles and the porous ceria microparticles (al) [microparticles (ai)] is not particularly limited, and the microparticles (al) may be used. And a binder (c) and a solvent (B) composed of water and/or an organic solvent are mixed and produced, and from a practical viewpoint, the fine particles (al) are dispersed in the dispersion solvent (b). A method of mixing and producing a titanium-containing sol (als), the above-mentioned binder (c), and a solvent (B) made of the above water and/or a solvent is preferred. The surface containing the surface is modified with a titanate-based compound. 317388 39 1266752. The manufacturing method of the ink-receiving layer-forming applicator for the perforated-oxidized oxide particles (a2) [microparticles (a2)] is not particularly The limitation is that the above-mentioned microparticles (10), the binder (6), and the solvent (B) composed of water and an organic solvent are mixed, manufactured, and 'from the solid point of view, the microparticles (10) are divided into months. A method of mixing and producing a titanium-containing sol (4), a binder, c, and a solvent (8) made of the above water and/or an organic solvent, which is formed by Knife &gt; It is ensured that the fluidity of the application liquid for forming the ink receiving layer is not required to be added again by water and/or when the above-mentioned dispersion solvent (8) is contained in the titanium sol or the above-mentioned titanium sol. Solvent (B) made from organic gluten. The mixing operation of each of the above components is usually carried out using a device such as a drum, a drum type disperser, a three-unit machine, or a strong-energizer sand mixer. It is preferable to form a sheet for recording a w-water double layer with a sheet-like substrate (hereinafter referred to as "an ink-receiving layer of a substrate substrate"). There is no special restriction 'use Ρ £τ, gasified olefins, etc. 2: use: plain paper, various paper, steel plate, cloth, etc. These substrates can be used after being treated with a non-use base (Makizaki). The above-mentioned titanium dioxide fine particles and the above surface-modified multi-milk-cut microparticles (8) may be primary particles 317388 40 1266752 secondary particles, and the primary particles may be mixed with secondary particles. ;: two = two particles in the application solution is not easy to monodisperse into - sub-particles = set of particles. Also, the primary particles may be contained in one particle. The method of forming the ink receiving layer on the substrate can be as long as the type of the corresponding substrate is used. The substrate for recording the ink-receiving layer can be specifically coated by the coating liquid for forming the receiving layer by the mist method, the _ κ coating method, the " η squeegee coating method, the bar coating method, and the i coating method. It is formed by drying on the surface of the substrate. Further, 'the substrate for recording the ink-receiving layer can be ΐ=Τ2) dispersed in water and the solvent of the machine = the coating liquid is applied to the surface of the substrate, and the dried metal compound is carried on the microparticles (the refinement) The surface of the microparticles (10) is formed. For example, it is necessary to add a solution of the cationic hydrated compound to the solution, such as a fog method, a slit method, a plate coating method, a bar coating method, a coating method, or the like. After the substrate is supported, the cationic aquarium metal compound is supported on the surface of the fine particles (al) or the fine particles (4). The cationic hydrated metal compound is, for example, A12(0H)C1: the amount of the support is cationic. The weight ratio of the hydrated metal compound to the oxide particles (the cationic hydrated metal compound, the above fine particles (8) or the above fine particles (8)))) is preferably in the range of from 5 to 0.2. In this case, the ratio of the cationic hydrated metal compound to the above-mentioned fine particles (al) or the above-mentioned fine particles may be a concentration within the above range, and the concentration of the cationic water 5 metal compound solution is not particularly limited. 317388 41 1266752 Drying can be carried out repeatedly. The ink receiving layer thus formed is generally preferably at least fine pores having a pore diameter in the range of from 3. 4 to 2,000 nm, even when any of dye-based inks or pigment-based inks is used. The pore volume of the pores having a pore diameter of 3·4 to 30 nm is in the range of 〇·2 to 3〇ml/g or the pore volume of the pores having a pore diameter of 30 to 2,0〇〇nm is 〇· The range of ΐ to 2.5 ml//g is preferred. If the pore volume of the pores having a pore diameter of 3.4 to 30 nm is less than 2 ml / g, the absorption capacity of the ink is small, and it will ooze out, and the sharpness and high precision cannot be obtained. In addition, if the pore volume of the pores having a pore diameter of 3.4 to 3 〇 nm is larger than 3.0 ml/g, the fixability of the dye is lowered, and the strength of the ink receiving layer is lowered. If the pore volume of the pores having a pore diameter of 30 to 2,0 〇〇nm is less than 2.5 ml/g, then The ink is not sufficiently absorbed, and the pigment particles remain on the surface of the receiving layer and are peeled off by abrasion. The ink receiving layer is used for recording, and the material is discolored. The pore diameter is 3〇 to 2, and the pores of 〇〇〇nm are When the volume of the fine 9-hole is more than 2.5 ml/g, the fixing property of the pigment particles is lowered, and the pigment particles are often accumulated in the lower portion of the ink receiving layer (near the surface of the substrate) after printing, and the substrate for recording the ink receiving layer is attached. The thickness of the ink receiving layer formed on the substrate may be arbitrarily set according to the thickness of the substrate, the use of the brush, and the type of printing ink, usually at &quot; to 1〇〇 / ^ _ is ideal. If the thickness of the ink receiving layer is less than · 5 · the absorption capacity of the ink is insufficient to cause oozing, and when the ink is used 317388 42 1266752 j, the color will decrease. The thickness ratio is 100/2 m. The thick ink receiving layer, the =k wipe is not easy to obtain the inch, and it needs to be applied a plurality of times, causing the economic problem 'cracking and peeling when applied and dried. The decoloring property is also deteriorated. The above ink receiving layer per Fine unit weight The pore volume is a value measured by a mercury intrusion method as follows: (1) A weight-receiving sheet and an ink-receiving layer are attached to an ink-receiving layer, and a sheet for a force of 0.2 to 0.3 g is inserted into the measuring unit (〇5cc). Volume), using the aut〇SCAN 6〇porpsimeter manufactured by QUANTA CHROME, the mercury contact angle is l3G. The mercury surface tension is 473dy:/m2', the measurement range is set to "high pressure", and the pore distribution is measured. The pore distribution of the pores of the pores having a pore diameter of 3 4 to 3 〇 nm and the pore volume of the pores having a pore diameter of 3 G to 2,0 (K) nm are measured from the measurement. The weight of the receiving layer in the film seeks to pick up

之細孔容積。 S i色方法： _於本發明附有墨水接受層記錄用基材，經由喷墨印 進行印子或印圖後進行紫外線照射、與酸性氣體 六氧接觸，可將該印字或印圖消色。 /等方法中以妝射紫外線較佳。紫外線照射時之光 /牛κ銀k、金屬鹵素燈、鎵燈、水銀氣燈、閃光燈等 、、二由太陽光照射亦有效果。紫外料之照射裝置對應i 面積、照射線量等’只要選擇掃描型、非掃描型之任何· 種即可’照射條件只要對應將印字或印圖分解必要之照』 此源決定照射寬度等即可。又，接觸之上述酸性氣體形 317388 43 1266752 so2氣體、co2氣體等。 消色效果之程度根據上述消色方法（紫外線照射、與酸 性氣體或臭氧接觸）提供之時間作適當之調整。 上述印字或印圖使用之墨水只要能經由上述消色方法 獲得消色效果之墨水即可，並無特別之限制，亦可使用含 有染料之墨水、含有顏料之墨水； 含有染料之墨水，較佳列舉含有下述染料之墨水： C.LSolvent Black27 ^ C.I.Solvent Black28 ^ C.I.Solvent • Black22、C.I.Solvent Black29、C.I.Solvent Red83-1、 C.LSolvent Redl25 - C.LSolvent Redl32 &gt; C.LSolvent Blue47-C.I.Solvent Blue48'C.LSolvent Blue70^ C.I.Solvent Yellow88、C.I.Solvent Yellow89、C.I.Basic Violetl、 C.I.Basic Violet3 &gt; C.I.Basic Redl &gt; C.I.Basic Red8 &gt; C.I.Basic Black2、Basic Blue5、Basic Blue7、Basic Violetl、Basic VioletlO、Basic Orange22、Basic Red :1、 • Basic Yell owl'Basic Yellow2、Basic Yell ow3 等驗性染料。 其他可使用微生物生出之天然色素，經由紫外線顯示 消色性之色素。該等天然色素之例列舉紅麴色素等。 該等染料之溶劑列舉曱基乙基甲酮、丙酮、環己酮等 酮類；甲醇、乙醇、異丙醇等醇類；溶纖劑、丁醯基溶纖 劑等醚類；乙二醇、二乙二醇、三乙二醇、丙二醇、己二 醇等伸烷二醇類；乙二醇曱醚、二乙二醇曱醚、三乙二醇 一甲醚、二乙二醇乙醚、三乙二醇一乙醚等多元醇之烷基 醚類；甘油、聚乙二醇、聚丙二醇等聚伸烷二醇類；N_曱 44 317388 1266752 . 基-2:比咯烷酮、u_二f基_2_咪唑烷酮等含氫雜環_類; 離子交換水等，該等可單獨使用！種，亦可2種以:、’ 使用。 个X上k合 含顏料之墨水可使用將顏料用分散劑分散於 分散劑廣泛使用界面活性劑等。顏料可使用 ：： 系顏料或無機系顏料。 友有機系顏料列舉偶氮顏料（例如偶氮色澱顏料、不溶性 偶氮顏料、縮合偶氮顏料、螯合偶氮顏料等）、多 ' ?£^(perynone)|I# , ^謂顏料、硫彀顏料、異卿滿.1 _酮顏料、 性染=養合物等)、硝摘、亞 觸法ΓΪί顏料除了氧化欽及氧化鐵之外，可列舉經由接 _ 回酿爐法、熱法等公知之方法製造之碳黑，且體而 吞列舉爐法碳黑、燈黑、乙炔黑或 们雜虹 77)類等。 寻反黑（C·1·顏料黑 [實施例] 不口 據實施例對本發明加以說明，但是本發明並 个&quot;、限於該等實施例。 &lt;評估方法〉 積： 二氧化矽微粒子之比表面積A 燥機乾焊德# 1積為對於將矽溶膠用凍結乾 定事置' Λ 小時之試料，使用比表面積測 衣置u淺愛歐尼斯公司製造，「multis〇ivei2」）’經由 317388 45 1266752 氮吸附法（BET法）測定。 平均粒子徑： 二氧化矽微粒子之平均粒徑經由使用粒徑分布測定裝 置（Particle Sizing Systems 公司製造：「NICOMP MODEL 3 8 0」），經由動態光散射法測定。 表面電荷量： 二氧化矽微粒子之表面電荷量為使用流動電位測定機 (MUTEK公司製造：PCD02)，調製氧化物（Si02+MOx)之濃 參度為1重量％之二氧化矽-氧化鋁改質微粒子之純水分散 體，注入測定容器，粒子電荷使用具有相反電荷之聚合物 ，進行由滴定測定。負電荷之二氧化石夕微粒子使用0.001N 聚-DADMAC(陽離子性高分子電解質）作為聚合物標準 液，進行滴定。 組成分析： 鈦、鋁、鈉及矽之含量經由下述之方法測定。 Φ [1]鈦、鋁之含量（換算為Ti〇2、Al2〇3含量） 進行如下所示之前處理，用ICP發光分析裝置（精工儀 器公司製造之SPS1200A型）測定。 1) 採取含有鈦酸酯之矽溶膠約5g放在鉑皿上。 2) 在砂浴上乾固，用1000°C電氣爐燒成約1分鐘。 3) 加入硫酸（1 + 1 )2ml及氳氟酸10ml，在砂浴上加熱至 發出硫酸之白煙為止後用蒸餾水稀釋成100ml。 [2]鈉含量（換算為Na20之含量） 進行與上述[1]相同之前處理，用原子吸光光度計（曰 46 317388 1266752 立公司製造Z-5300型）測定。 [3]矽含量（換算為SiCh含量） 測定將含有鈦酸酯之矽溶膠在1 〇〇〇°C加熱1小時後之 重量（固體成分重量）。進行與上述[1]及[2]之方法相同之操 作，尋求固體成分中Ti〇2、a12〇3及Na20之合計含量，將 該值從固體成分全體重量除去，作為Si〇2之含量。 [多孔質一氧化發微粒子之調製] 石夕溶膠之調整： 水 釋 將球狀I谷膠Al(二氧化石夕平均粒徑為3Qnm，溶劑為 固體成分濃度為19.9重量％)351kg用純水i2〇kg稀 攪拌10分鐘，調製固體忐 J衣口體成分濃度為4.5重量％之水性 梦溶谬。該水性梦溶职φ 4 或W曰、U 0 加入水玻璃318层，將？11值調整 為11後歼 &gt;皿至9 8 C，於9 s ^士 &amp; y8C保持15分鐘。 添加稀釋欲 將矽酸鈉水溶液（Si〇 換樹脂中通液，進行陽'^為4.9重量％)在陽離子交 量0/。之石夕酸液U.〇kg。於^交換’獲得Si〇2濃度為4.8重 製Si〇2濃度為3〇重旦〆矽酉夂液中添加純水6.52kg，調 性石夕溶膠中，於98。〇、6之=釋石夕酸液。接著，在上述水 時。接著冷卻至40°C以下，獲 得固體成分濃度為4·8 T丧者； 重里 ％、3 S /cm、於31.8°C之卩^值 ·9(：之傳導度為1.819mS ”、、1〇·53之矽溶膠26· 17.5kg，再於981：保持} j日守間添加上述稀釋矽酸液 cm 8kg 脫|g處理： 317388 47 1266752 在上述步驟獲得之矽溶膠l〇 〇kg中在！分鐘以内之時 間添加35%鹽酸613g，攪拌1〇分鐘，將二氧化矽微粒子 中之鋁離子溶出，作為浸出品。接著用超膜（旭化成（股）公 司製造，SIP-1013)進行一次濃縮至浸出品之固體成分濃度 成為2倍為止。將該經濃縮之矽溶膠使用相同之超膜，邊 ^夜面保持疋邊在5小時將該液體用·0之稀釋鹽 酸洗淨，再用純水洗淨至母液之PH值成為3·〇為止，作A 純水洗淨品。 作马The pore volume. S i color method: The substrate for ink-receiving layer recording is attached to the present invention, and after printing or printing by inkjet printing, ultraviolet irradiation is performed and contact with acid gas hexaoxide, and the printing or printing can be achromatic. In the method of /etc. Light when irradiated with ultraviolet light / cow κ silver k, metal halide lamp, gallium lamp, mercury gas lamp, flash lamp, etc., and the second is also effective by sunlight. The irradiation device for the UV material corresponds to the i area, the amount of the irradiation line, etc. 'As long as the scanning type or the non-scanning type is selected, the irradiation condition is as long as it is necessary to decompose the printing or the printing." . Further, the acid gas is in contact with the above-mentioned acid gas type 317388 43 1266752 so2 gas, co2 gas or the like. The degree of decoloring effect is appropriately adjusted according to the time provided by the above-described decoloring method (ultraviolet irradiation, contact with an acid gas or ozone). The ink used for the printing or printing may be any ink which can obtain a decolorizing effect by the above-described decoloring method, and is not particularly limited, and an ink containing a dye or an ink containing a pigment may be used; and an ink containing a dye is preferable. List the inks containing the following dyes: C. LSolvent Black27 ^ CISolvent Black28 ^ CISolvent • Black22, CISolvent Black29, CISolvent Red83-1, C.LSolvent Redl25 - C.LSolvent Redl32 &gt; C.LSolvent Blue47-CISolvent Blue48'C.LSolvent Blue70^ CISolvent Yellow88, CISolvent Yellow89, CIBasic Violetl, CIBasic Violet3 &gt; CIBasic Redl &gt; CIBasic Red8 &gt; CIBasic Black2, Basic Blue5, Basic Blue7, Basic Violetl, Basic VioletlO, Basic Orange22, Basic Red: 1, Basic Yell owl'Basic Yellow2, Basic Yell ow3 and other test dyes. Other natural pigments which are produced by microorganisms can be used to display achromatic dyes via ultraviolet rays. Examples of such natural pigments include red peony pigments and the like. Examples of the solvent of the dyes include ketones such as mercaptoethyl ketone, acetone, and cyclohexanone; alcohols such as methanol, ethanol, and isopropanol; ethers such as cellulolytic agents and cellosolve; and ethylene glycol and Ethylene glycol such as ethylene glycol, triethylene glycol, propylene glycol or hexanediol; ethylene glycol oxime ether, diethylene glycol oxime ether, triethylene glycol monomethyl ether, diethylene glycol diethyl ether, triethyl Alkyl ethers of polyhydric alcohols such as diol monoethyl ether; polyalkylene glycols such as glycerin, polyethylene glycol, polypropylene glycol; N_曱44 317388 1266752. Base-2: pyrrolidone, u_two f a hydrogen-containing heterocyclic group such as a base-2_imidazolidinone; ion-exchanged water, etc., which can be used alone! Species can also be used in two types: , ' For the X-k-containing pigment-containing ink, a pigment dispersant may be used for dispersing the dispersant, and a surfactant or the like may be widely used. Pigments can be used with :: pigments or inorganic pigments. Friends organic pigments cite azo pigments (such as azo lake pigments, insoluble azo pigments, condensed azo pigments, chelated azo pigments, etc.), more '?? (perynone)|I#, ^ said pigments, Thionine pigments, sulphur pigments, ketone pigments, dyes, sucrose pigments, etc., nitrites, nitrites, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate, sulphate The carbon black produced by a known method is exemplified by a furnace black, a black, an acetylene black or a genus 77). Anti-Black (C·1·Pigment Black [Examples] The present invention will be described by way of examples, but the invention is not limited to the examples. <Evaluation method> Product: cerium oxide microparticles Specific surface area A Drying machine Dry welding #1 is a sample for the purpose of setting the sol-gel to freeze-drying, and using the specific surface area to be placed in the U-Anis company, "multis〇ivei2") 317388 45 1266752 Determination by nitrogen adsorption method (BET method). Average particle diameter: The average particle diameter of the cerium oxide microparticles was measured by a dynamic light scattering method using a particle size distribution measuring apparatus (manufactured by Particle Sizing Systems, Inc.: "NICOMP MODEL 380"). Surface charge amount: The surface charge amount of the cerium oxide microparticles was changed using a flow potential measuring machine (manufactured by MUTEK Co., Ltd.: PCD02), and the concentrated oxide of the oxide (Si02+MOx) was adjusted to 1% by weight of cerium oxide-alumina. A pure aqueous dispersion of the fine particles is injected into the measurement container, and the particle charge is measured by titration using a polymer having an opposite charge. The negatively charged silica fine particles were titrated using 0.001 N poly-DADMAC (cationic polymer electrolyte) as a polymer standard solution. Composition Analysis: The contents of titanium, aluminum, sodium and cesium were determined by the following methods. Φ [1] The content of titanium and aluminum (converted to Ti〇2 and Al2〇3 content) was measured by the following procedure and measured by an ICP emission spectrometer (SPS 1200A manufactured by Seiko Instruments Inc.). 1) Approximately 5 g of a cerium sol containing titanate was placed on a platinum dish. 2) Dry on a sand bath and fire in an electric furnace at 1000 ° C for about 1 minute. 3) 2 ml of sulfuric acid (1 + 1 ) and 10 ml of hydrofluoric acid were added, and heated to a white smoke of sulfuric acid on a sand bath, and then diluted to 100 ml with distilled water. [2] Sodium content (converted to Na20 content) The same treatment as in the above [1] was carried out, and it was measured by an atomic absorption spectrophotometer (Z-5300 model manufactured by 曰46 317388 1266752). [3] 矽 content (converted to SiCh content) The weight (solid content weight) of the cerium sol containing titanate after heating at 1 ° C for 1 hour was measured. The operation similar to the methods of the above [1] and [2] was carried out, and the total content of Ti〇2, a12〇3, and Na20 in the solid content was sought, and the value was removed from the total weight of the solid component to obtain the content of Si〇2. [Preparation of Porous Oxidized Microparticles] Adjustment of Shixi Sol: Water release will be spherical I gluten Al (the average particle diameter of the dioxide dioxide is 3Qnm, the solvent is a solid concentration of 19.9% by weight) 351kg with pure water I2〇kg was stirred for 10 minutes, and a water-based dream solution having a solid content of 4.5% by weight of the mouthwash was prepared. The water-based dream job φ 4 or W 曰, U 0 added 318 layers of water glass, will? The 11 value is adjusted to 11 歼 &gt; dish to 9 8 C, for 9 minutes at 9 s ^ & y8C. To add a dilution, a sodium citrate aqueous solution (Si 〇 was exchanged for the resin, and the cation was 4.9 wt%) at a cation exchange rate of 0/. Shixi acid U.〇kg. The concentration of Si〇2 was 4.8 and the concentration of Si〇2 was 4.8. The concentration of Si〇2 was 3. 5 kg of pure water, and the amount of pure water was 6.52 kg. 〇, 6 = 释石夕酸液. Next, at the time of the above water. Then, it was cooled to 40 ° C or lower to obtain a solid concentration of 4·8 T; the weight %, 3 S /cm, and the value of 31.8 ° C·9 (the conductivity was 1.819 mS ”, 1 〇·53 矽 sol 26· 17.5kg, then at 981: keep} j day sputum added the above diluted citric acid solution cm 8kg off | g treatment: 317388 47 1266752 obtained in the above procedure 矽 〇〇l〇〇kg 613 g of 35% hydrochloric acid was added in a minute or less, and the aluminum ions in the cerium oxide microparticles were eluted as a leaching product by stirring for 1 minute, and then concentrated by a super membrane (as manufactured by Asahi Kasei Co., Ltd., SIP-1013). The concentration of the solid component of the leaching product is doubled. The concentrated bismuth sol is used in the same ultra-thin film, and the liquid is washed with a diluted hydrochloric acid of 0 at 5 hours, and then pure. Wash the water until the pH of the mother liquor becomes 3 〇, and wash it as A pure water.

接著，進行2次濃縮，濃縮至成為2倍純水洗淨 ^ 工取勺z货純水洗淨品Then, concentrate twice, concentrate to 2 times pure water, wash it, take a spoon, and wash the pure water.

分丨農度為止。獲得之發溶膠（以下稱為「破溶膠則」 二氧化矽之比表面積及經進行與上 相:丨 ::):=^及納之含量(各個為換=:Divided into farms. The obtained sol (hereinafter referred to as "broken sol" cerium oxide has a specific surface area and is subjected to the upper phase: 丨::::=^ and the content of the sinter (each is changed =:

317388 48 1266752 .317388 48 1266752 .

[表3] 表1' 平均粒徑 比表面積 Si〇2 AI2O3 Na20 [nm] [m2/g] J [重量％] [重量％] [重量％] 石夕溶膝Β3 25 523 12.0 0.1 0.01 球狀紗溶膠A3 25 250 15.0 4.7 2.73[Table 3] Table 1 'Average particle size specific surface area Si〇2 AI2O3 Na20 [nm] [m2/g] J [% by weight] [% by weight] [% by weight] Shi Xirong knee Β 3 25 523 12.0 0.1 0.01 Sphere Yarn sol A3 25 250 15.0 4.7 2.73

Na20Na20

[重量％] [重量％] [重量°/〇] [重量%] 5.2 0.02 2.53[% by weight] [% by weight] [% by weight/〇] [% by weight] 5.2 0.02 2.53

Na20 0.03 2.84 於上述多孔質二氧化石夕微粒子之調製步驟，邊參考日 本專利特開2GG1-233611號公報揭示之方法邊經由將成為 原料之球㈣溶膠之平均粒徑、同—㈣膠之組成、脫銘 處理之條件作適當之設定，亦即使用平均粒徑為25麵、 、或12〇nm之球狀矽溶膠作為原料使用，其他以上述 =件為基準’ δ周製固體成分濃度為12重量％、分散溶劑為 j醇等各㈣轉（25nm、8Gnm或i2Qnm)。各料膠中 :乳化石夕微粒子之特性如表W至表W、表2及表3所 夕,=_ Γ均粒徑為1nm之球狀石夕溶膠A2(表卜2)不適用 二質二氧化韻粒子之調製步驟，供給以下之實驗。Na20 0.03 2.84 In the above-mentioned preparation process of the porous silica dioxide granules, the method of the method disclosed in Japanese Patent Laid-Open No. 2GG1-233611, the average particle diameter of the sol which will become the raw material, and the composition of the same (four) rubber The conditions for the de-ming treatment are appropriately set, that is, the spherical cerium sol having an average particle diameter of 25 faces, or 12 〇 nm is used as a raw material, and the others are based on the above-mentioned = part. 12% by weight and the dispersion solvent was each (iv) rotation (25 nm, 8 Gnm or i2 Qnm) such as j alcohol. In each material glue: the characteristics of the emulsified stone particles are as shown in Table W to Table W, Table 2 and Table 3, and the spherical granules A2 (Table 2) with the average particle size of 1 nm are not applicable. The preparation step of the dioxin particles was supplied to the following experiment.

巧二由^氧化鈦微粒子、多孔質二氧切微粒子及分散溶 4組成之含有鈦之矽溶膠J 317388 49 1266752 [實施例1 - 1至1 -7、比較例1 - 1色1 -61 在表2所示之各矽溶膠300g中加入 固體成分濃度：10重量％、 二氧化鈦平均粒徑：l〇nm、 分散溶劑：異丙醇、以及 結晶型：銳鈦礦型 之鈦溶膠，使成為表2表示之矽與鈦之重量比（換算為Si〇2 /Tl〇2)，攪拌混合，調製含有鈦之矽溶膠。 U周製用酞酸醋糸化合物進行表面修飾所成之多孔質二氣 化矽微粒子及分散溶劑組成之含有鈦之矽溶膠] 施例2-1至2-7、比較例2·〗至2-6&quot;! 於常溫，在1分鐘於表3表示之各矽溶膠3〇〇g中加入 酞酸酯系化合物（普煉刻德（商標登記）KR-44，味之素（股） 公司製造，化合物名稱··異丙基三（N_胺基乙基_胺基乙基） 酞酸酉旨）後在常溫擾拌2小時、混合，獲得含有鈦之石夕溶 φ膠。添加於各矽溶膠之鈦酸酯系化合物之重量及所声得含 有鈦之石夕溶膠中之石夕與鈦之重量比（換算為叫/^2)表 LXMJiLIzll 二了使用四異丙氧基鈦酸醋替代上述鈦酸醋化合物 (曰煉商標登記)KR_44)外，進行與上述實施例2_3 醋李Hi獲得含核巧轉。添加於切溶膠之鈦iA titanium-containing cerium sol consisting of titanium oxide microparticles, porous dioxygen microparticles, and dispersion dissolving 4 J 317388 49 1266752 [Examples 1 - 1 to 1 -7, Comparative Example 1 - 1 color 1 - 61 The solid content concentration of 10 g of each cerium sol shown in Table 2 was 10 wt%, the average particle diameter of titanium dioxide: l 〇 nm, a dispersing solvent: isopropyl alcohol, and a crystalline type: anatase type titanium sol, which became a table 2 is a weight ratio of bismuth to titanium (converted to Si〇2 / Tl 〇 2), and stirred and mixed to prepare a cerium sol containing titanium. A titanium-containing cerium sol composed of a porous bismuth hydride fine particle and a dispersion solvent formed by surface modification with a bismuth citrate hydrazine compound] Examples 2-1 to 2-7, Comparative Example 2 〗 〖2 -6&quot;! At room temperature, a phthalate-based compound (Krypton (trademark)) KR-44, manufactured by Ajinomoto Co., Ltd., was added to each 矽Sol 3 〇〇g shown in Table 3 at 1 minute. After the compound name, isopropyl tris(N-aminoethyl-aminoethyl) ruthenate was used, it was stirred at room temperature for 2 hours, and mixed to obtain a titanium-containing yttrium-containing yttrium. The weight ratio of the titanate compound added to each bismuth sol and the weight ratio of the stellite to titanium in the sol-sol containing the titanium (converted to be called /^2). LXMJiLIzll In addition to the above-mentioned titanic acid vinegar compound (Kelly Trademark Registration) KR_44), the titanate was obtained in the same manner as in the above Example 2_3. Titanium added to the cut sol

Him重量及所㈣含核之㊉轉w與欽之: (奐斤為Si〇2/Ti〇2)表示於表3。 317388 50 1266752 [抗污被膜形成用組成物之調製] 將實施例1-1調製之各含有鈦之矽溶膠100§與纖維素 黏合劑（乙基纖維素水溶液、固體成分濃度5重量％)混合， 使固體成分之重量比成為含有鈦之矽溶膠\纖維素黏合劑 =75 : 25，調製抗污被膜形成用組成物。 對於貫施例1-2至1-7及比較例1-1至1_6、實施例n 至2_7及比較例2-1至2-6、實施例3-1調製之各個含有鈦 之矽溶膠進行與實施例丨“調製之各含有鈦之矽溶膠相同 之操作’调製抗污被膜形成用組成物。 废止水中生物附荖之詖龄 : 將配合實施例1-1製造之含有鈦之矽溶膠之抗污被膜 形成用組成物及配合實施例2-1製造之含有鈦之矽溶膠之 抗污被膜形成用組成物，各別浸潰於聚乙烯製網材10分 鐘，塗抹、風乾。上述組成物之塗抹量，在乾燥後之重量 對於網100 f量分各別4 i重4分。將該等網材及未塗抹 籲抗污被膜形成用組成物之網材浸潰於恆溫水槽（3〇。〇，在 自然光之環境放置3個月後從水槽中取出。塗抹抗污被膜 形成用組成物之2個網材與未塗抹抗污被膜形成用組成物 之網材比較，可顯著抑制水苔繁茂。 if垢分解贫驗： 將如上所述調製之各抗污被膜形成用組成物用棒塗 後’在音通紙單面塗抹5g/m2之量，於8〇。〇乾燥，獲得 形成抗污被膜之附有墨水接受層之普通紙。又。每丨^普 通紙塗抹1種類抗污被膜形成用組成物。 317388 51 1266752 將具有該等抗污被膜之附有墨水接受層之普 ，室測試機内（容積6〇L)，用3根 ： /根動3分鐘，煙粒子附著於紙表面；^里= 小型，帶型UV照射裝置(曰本電池(股)公二^ 二用：壓水銀燈照射紫外線，測定至污垢分解為止之時 間。该結果表示於表2及表3。 、 «室測試機内充滿臭氧氣體，放置附有 子，呈污穗狀態之紙，測定將污： 果表示於表2及表3。 ^❹間。其結 將 &gt;可垢分解為止之時間為將 煙粒子’呈現污機狀態之普通紙之顏色:使=面:著 形成用組成物，作為對照用之附有墨水接==膜 顏色（白色）用目；^、仓&gt; L &gt; 曰 9通、、、氏之 麵仃錄，至成為同樣顏色為止之時間。The weight of Him and the (4) nuclear-containing ten-turn w and the zhizhi: (奂斤为Si〇2/Ti〇2) are shown in Table 3. 317388 50 1266752 [Preparation of composition for forming anti-fouling film] Each titanium-containing cerium sol 100 § prepared in Example 1-1 was mixed with a cellulose binder (ethyl cellulose aqueous solution, solid content concentration: 5% by weight) The weight ratio of the solid content was changed to a titanium-containing cerium sol/cellulose binder = 75:25 to prepare a composition for forming an anti-fouling film. For each of the titanium-containing cerium sols prepared in Examples 1-2 to 1-7 and Comparative Examples 1-1 to 1_6, Examples n to 2_7, and Comparative Examples 2-1 to 2-6 and Example 3-1 The composition for forming an antifouling film was prepared in the same manner as in the "modulation of each of the titanium-containing cerium sols prepared." The age of the biodegradable film was abolished: The titanium-containing cerium sol produced in accordance with Example 1-1 was prepared. The anti-fouling film-forming composition and the anti-fouling film-forming composition containing the titanium-containing cerium sol produced in Example 2-1 were each immersed in a polyethylene mesh material for 10 minutes, spread, and air-dried. The amount of the smear of the object, the weight after drying is 4 points for the net 100 f, and the net material of the composition is not immersed in the constant temperature water tank (3). 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 在 在 在 在 在 在 在 在 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然 自然If the moss is luxuriant. If the scale is decomposed, the composition of each anti-fouling film prepared as described above is formed. After coating with a bar, apply a 5 g/m2 on the single side of the fluent paper at 8 〇. Dry it to obtain a plain paper with an ink-receiving layer on the anti-fouling film. Also, apply it to each plain paper. A type of composition for forming an antifouling film. 317388 51 1266752 A chamber tester (volume 6 〇L) having an ink receiving layer attached to the antifouling film, using 3: /rooting for 3 minutes, smoke particles Attached to the surface of the paper; ^ Li = small, belt type UV irradiation device (曰本电池(股) 公二^ Two uses: The mercury lamp is irradiated with ultraviolet light to measure the time until the dirt is decomposed. The results are shown in Table 2 and Table 3. , «The chamber test machine is filled with ozone gas, and the paper with the attached state is placed in the state of the stained ear. The stain is measured. The results are shown in Table 2 and Table 3. ^❹. The knot will be the time until the scale is decomposed. The color of plain paper in which the smoke particles are present in a dirty state: the = surface: the composition for formation, and the ink for the control is attached == film color (white); ^, 仓&gt; L &gt ; 曰 9 通 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,

317388 52 1266752 • ⑩ 消色性試驗 臭氧接觸 消色所需 時間 1 1 1 1 如 Ο (N rn 1 I 1 1 1 紫外線照射 (光強度： 600mJ/cm2) 消色所需 時間 I νο 〇〇 v〇 r^i 1 1 1 1 — 1 2(外觀白濁） 1 〇〇 Φ 臭氧接觸 污垢分解 丨所需時間 I 1 1 1 1 o ο (N 1 1 1 紫外線照射 (光強度：600 mJ/cm2) 污垢分解所 需時間 I 8 6276 10 r4 1 1 1 : \〇 含有鈦之I 矽溶勝1 Si02/Ti02 6000 5688 6472 議 6276 I 5688 6472 一 m 00 6276 j -1 20000 30000 鈦溶膠| ΦΊ Ufiui η〇Π 3 0.060 0.057 0.063 0.055 0.060 0.057 0.9 1 0.063 0.9 | 0.055 S m 1.1 I 0.443 0.057 0.018 ' | 0.012 f 1藥、 、给 ， 1 [ • ) ， 丨 \ 二氧化矽微 粒子中之鋁 濃度(*) [重量%1 (N 〇\ ON ON (N On Ο) — 二氧化矽之 表面電何量 [&quot;eq/g] 〇 (N IT) S o 〇 CN yr\ s § s s 二氧化矽微 粒子之比表 面積 1 1 I o 700 m (N 8 v〇 1 1 § § 8 v〇 8 VD 二氧化矽微 粒子之平均 粒徑 I 一 &lt;N g § 一 (N g § g g g § S 固體成 分濃度 [重量%] 1 (N (N &lt;N CN fN fN fN fN (N &lt;N CN ΓΝ CN tm 編號 &lt; CQ u Q ti. o X — 2 J Π 比較例N1 實施例1-1 L實施例1-2 J 比較例1-2 比較例1-3 實施例1-3 實施例1·4 比較例1·4 比較例1-5 實施例1-5 實施例1-6 實施例1-7 比較例1&gt;6 ooi xs¥ois +i¥oJV)\¥¥oJVlr^I5)。m^^I'oiv^HfTvwi^-B^^^^sfu) 53 317388 1266752317388 52 1266752 • 10 Achromaticity test Time required for ozone contact decolorization 1 1 1 1 如Ο (N rn 1 I 1 1 1 UV irradiation (light intensity: 600mJ/cm2) Time required for color reduction I νο 〇〇v 〇r^i 1 1 1 1 — 1 2 (appearance is turbid) 1 〇〇Φ Time required for ozone to contact with scale decomposition I 1 1 1 1 o ο (N 1 1 1 UV irradiation (light intensity: 600 mJ/cm2) Time required for soil decomposition I 8 6276 10 r4 1 1 1 : \〇I containing titanium I 矽 胜 1 Si02/Ti02 6000 5688 6472 Discussion 6276 I 5688 6472 one m 00 6276 j -1 20000 30000 Titanium sol | ΦΊ Ufiui η 〇Π 3 0.060 0.057 0.063 0.055 0.060 0.057 0.9 1 0.063 0.9 | 0.055 S m 1.1 I 0.443 0.057 0.018 ' | 0.012 f 1 drug, , give, 1 [ • ) , 丨 二 二 二 二 二 ( ( ( ( ( ( [%%1 (N Ο\ ON ON (N On Ο) — What is the surface charge of cerium oxide [&quot;eq/g] 〇(N IT) S o 〇CN yr\ s § ss TiO2 particles Specific surface area 1 1 I o 700 m (N 8 v〇1 1 § § 8 v〇8 VD average particle size of the cerium oxide particles I &lt;N g § 1 (N g § ggg § S solid concentration [% by weight] 1 (N (N &lt; N CN fN fN fN fN (N &lt; N CN ΓΝ CN tm number &lt; CQ u Q ti. o X — 2 J Π Comparative example N1 Example 1-1 L Example 1-2 J Comparative Example 1-2 Comparative Example 1-3 Example 1-3 Example 1·4 Comparative Example 1·4 Comparative Example 1-5 Example 1-5 Example 1-6 Example 1-7 Comparative Example 1&gt;6 ooi xs¥ois +i¥oJV)\¥¥oJVlr^I5).m^^I'oiv^HfTvwi^-B^^^^sfu) 53 317388 1266752

消色性試驗 臭氧接觸 消色所需 時間 I 1 1 1 1 卜 o m 1 I 1 1 1 1 紫外線照射 (光強度： 600mJ/cm2) 消色所需時間 I m Ον 〇 un 1 ! 1 1 OO rn 卜 o ο S (N 1 跛 φ a? 臭氧接觸1 污垢分解所需 時間 I 1 1 1 1 v〇 oo 1 1 1 1 1 i 紫外線照射 (光強度： 600mJ/cm2) 污垢分解所需 時間 ο VD g 1 1 i 6440 I - O VO R s | 6050 1 12 含有欽之 矽溶膠 Si0/Ti02 重量比 6050 6245 5660 6440 6050 6245 5660 一 OO 6276 I 20325 I 28455 鈦溶膠 eW allhil ψη 3 0.031 0.030 0.033 0.029 0.031 0.030 0.033 0.029 187.7 ' 0.231 0.030 9.23xl03 6.60x10'3 j 0.021 矽溶膠 1 签：ε $ ι _ '1輕 [重量％] rs ON o 〇N S o 〇\ o — = § - 〇· 二氧财 之表面電 荷量 [&quot;eq/g] ο S s o R ΓΝ s o s s s 二氧僻 微粒子之 比表面積 .1 1 S to 1 8 rr &lt;N i 1 1 1 i i i cn &lt;N yr\ 二氧娜 微粒子之 平均粒徑 I 一 CN g § 一 g § s s s g g rs φ [重 *%] fN (N CN (N (N (N (N CN (N (N (N ΓΝ CN tm 編號 cQ Xi Q *σ Of) X： 一 一 E c η 比較例2-1 實施例2-1 實施例2-2 比較例2-2 比較例2-3 實施例2·3 實施例24 比較例24 比較例2-5 實施例2-5 實施例2名 實施例2-7 比較例24 實施例3-1 οοι x(#¥ 营 sv)\_¥ SVS3) 。一»s sv sss0 54 317388 4 1266752 [墨水接受層形成用塗抹液之調製] 將只轭例1-1調製之各含有鈦之矽溶膠1〇〇g與纖維素 黏合劑（乙基纖維素水溶液、固體成分濃度5重量混合， =體成刀之重里比成為含有鈦之矽溶膠：纖維素黏合劑 75 . 25，調製墨水接受層形成用塗抹液。 對於貝施例1-2至1-7及比較例丨_丨至1-6、實施例 至2-7及比較例2_丨至2_6、實施例3_丨調製之各個含有鈦 之發溶膠進行與實施例調製之各含有鈦之石夕溶膠相同 之知作，調製墨水接受層形成用塗抹液。 ^將如上所述調製之各墨水接受層形成用塗抹液用棒塗 覆’在普通紙單面塗抹5g/m2之量，於8〇。〇乾燥，獲得 附有墨水接受層之普通紙。又。每i張普通紙塗抹工種類 墨水接受層形成用塗抹液。 [印刷] 九在所獲得附有墨水接受層之普通紙用純正之顏料墨水 &gt;及染料墨水，經由喷墨列印機（GRAPHTEC公司製造， Masterjet)，用黑色印刷圖案w(放滿2cm四方塊格之大 小，且粗約3mm之文字「w」）。 [消色處理] 在經印刷附有墨水接受層之普通紙用小型輸 UV照射裝置（日本電 .^ 燈照射紫外線，測定至上述圖案W消色為止之時間。該妗 果表示於表2及表3 〇 / 將髒室測試機内充滿臭氧氣體，放置未進行上述印刷 317388 55 1266752 之附有墨水接受；夕並 曰之曰通紙，測定至上述圖幸 之時間。其結果表示於表2及表3。 W色為止 至消色為止之時間為印刷上述圖案 射等方法消色、附右黑卜^ / 俊用糸外線照 月巴附有墨水接受層之普通紙 顏色與使用各墨水接為二、 上忒圖案W之 黑水接為厚夕並 又層成用塗抹液作為對照用之附有 為同樣顏色為止之時間。 仃比較，至成 [產業上之可利用性] 二吏明之含有鈦之靖，可在各種基材表面 以能之抗污被膜，可形成消色性優越之 船底塗料之表面塗層、备 】用作為 床材或纸等之著面二，、、、、、，罔用塗料或壁材、天花板材料、 河4、、、氏寺之表面處理劑之原料。Decolorization test Time required for ozone contact decolorization I 1 1 1 1 Bu om 1 I 1 1 1 1 Ultraviolet irradiation (light intensity: 600 mJ/cm2) Time required for color reduction I m Ον 〇un 1 ! 1 1 OO rn卜o ο S (N 1 跛φ a? Ozone contact 1 Time required for soil decomposition I 1 1 1 1 v〇oo 1 1 1 1 1 i UV irradiation (light intensity: 600mJ/cm2) Time required for decomposition of dirt ο VD g 1 1 i 6440 I - O VO R s | 6050 1 12 Containing sputum sol Si0/Ti02 Weight ratio 6050 6245 5660 6440 6050 6245 5660 One OO 6276 I 20325 I 28455 Titanium sol eW allhil ψη 3 0.031 0.030 0.033 0.029 0.031 0.030 0.033 0.029 187.7 ' 0.231 0.030 9.23xl03 6.60x10'3 j 0.021 矽Sol 1 Sign: ε $ ι _ '1 light [% by weight] rs ON o 〇NS o 〇\ o — = § - 〇· 二氧财之Surface charge amount [&quot;eq/g] ο S so R ΓΝ sosss The specific surface area of the dioxygenated microparticles.1 1 S to 1 8 rr &lt;N i 1 1 1 iii cn &lt;N yr\ Dioxa microparticles Average particle size I - CN g § a g § sssgg rs φ [weight *%] fN (N CN (N (N (N (N (N (N (N (N (N (N (N CNN No. cQ Xi Q *σ Of) X: one-to-one E c η Comparative Example 2-1 Example 2-1 Example 2-2 Comparative Example 2-2 Comparative Example 2-3 Example 2·3 Example 24 Comparative Example 24 Comparative Example 2-5 Example 2-5 Example 2 Name Example 2-7 Comparative Example 24 Example 3-1 οοι x (#¥ 营 sv)\_¥ SVS3). A »s sv sss0 54 317388 4 1266752 [Preparation of the ink-receiving layer-forming applicator] Each of the titanium-containing cerium sols prepared in the yoke example 1-1 was mixed with a cellulose binder (ethylcellulose aqueous solution, solid content concentration: 5 weights, = The ratio of the weight of the body to the knives is 矽 sol containing titanium: cellulose binder 75. 25, and the application liquid for forming the ink receiving layer is prepared. Titanium-containing sols for each of Bayes 1-2 to 1-7 and Comparative Examples 丨_丨 to 1-6, Examples to 2-7, and Comparative Examples 2_丨 to 2_6, and Example 3_丨The same applies to the titanium-containing sol-containing sol prepared in the examples, and the application liquid for forming an ink receiving layer was prepared. ^ Each of the ink-receiving layer-forming coating liquids prepared as described above was coated with a bar, and was applied to a single side of the plain paper in an amount of 5 g/m 2 at 8 Torr. The crucible is dried to obtain plain paper with an ink receiving layer. also. Each type of plain paper application type The ink receiving layer is formed with an application liquid. [Printing] Nine prints of pure pigment inks and dye inks for plain paper with an ink-receiving layer are obtained, and print patterns are printed in black by an inkjet printer (manufactured by GRAPHTEC, Masterjet) (filling 2 cm four The size of the square, and the text "w" is about 3mm thick. [Color-removing treatment] The time for printing the ultraviolet ray to the above-mentioned pattern W is measured by a small-sized UV irradiation device for plain paper with an ink-receiving layer (the Japanese electric lamp is irradiated with ultraviolet light). The results are shown in Table 2 and Table 3 〇 / The dirty chamber test machine is filled with ozone gas, and the ink is not received for the above printing 317388 55 1266752; the 曰 曰 曰 曰 , paper is measured and the time is shown to the above figure. The results are shown in Table 2 and Table 3. The time from the W color to the eradication is the method of printing the above-mentioned pattern, etc., and the right side is black, and the right side of the line is attached to the ink. The color of the plain paper with the ink receiving layer is the same as that of the ink. The black water of the upper pattern W is connected to the thick eve and the layer is formed with the application liquid as the control for the same color. 仃Comparative, Zhicheng [Industrial Applicability] It can be used as a surface coating for shipboard coatings with superior decolorization properties on the surface of various substrates, and can be used as a surface material for paper or paper, etc.涂料Use paint or wall material, ceiling Materials, 4, r ,,,'s temple surface treatment agent of raw materials.

317388 56317388 56

Claims (1)

1266752 十、申請專利範圍： 1· 一種含有鈦之矽溶膠 ⑷以下之微粒子⑻或微= ⑷)：平均粒徑為2至50二 平均粒徑為100nm :化鈦❹子及 在300mVg以上之w 法求得之比表面積 g以上之夕孔質二氧化矽微粒子， (a2) ··平均粒徑為5 u〇〇nm，經由 比表面積在30〇m2/g以上 卜 法求侍之 g 上之夕孔質二氧化矽微敕早矣 面用鈦酸酯系化合物進行表面修飾所成 = 化矽微粒子；及 貝一軋 (b)分散溶劑。 2.如申請專利範圍第丨項之含有鈦之料膠，其中， 鈦酸酯系化合物係以下述通式（1)至（3)之任一者表示. RUnTiR124.n ...........(1) 、不. [式中，η為1至4之整數； • n Rl1為碳原子數1至6之烷氧基，η=2或3時，2個 R 1可結合，形成下述通式（la)表示之環狀構造，亦可將 結合於通式（la)中鄰接氧原子之碳原子之一之2個氫原 子以氧原子取代，形成下述通式（lb)表示之環狀構造； R12為碳原子數1至5之烴基或下述通式（lc)、 (Id)、（le)、（If)、（lg)或（lh)表示之有機基； 317388 57 1266752 [化i] h2c——0、 (la) H2xCx—〇〆 (其中，x為1至7之整數）， [化2] 0=c— (lb) H2yCv- (其中，y為1至7之整數）， [化3] 0 II (lc) —0—C—CpH2p+1 (其中，P為4至30之整數）， φ [化 4] 〇 II 〇—Γ 0H1266752 X. Patent application scope: 1. A fine particle (8) or micro = (4)) containing titanium sol (4) or less: average particle diameter of 2 to 50 2 average particle diameter of 100 nm: titanium ruthenium and above 300 mVg The method of obtaining a specific surface area of g or more of uranium dioxide cerium oxide particles, (a2) · · average particle size of 5 u 〇〇 nm, via a specific surface area of 30 〇 m 2 / g or more The cerium porphyrin cerium oxide micro 敕 敕 敕 用 用 用 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛2. The titanium-containing material gum according to the invention of claim 2, wherein the titanate compound is represented by any one of the following general formulae (1) to (3). RUnTiR124.n ...... .....(1), No. [wherein, η is an integer from 1 to 4; • n Rl1 is an alkoxy group having 1 to 6 carbon atoms, and when η = 2 or 3, 2 R 1 may be The ring structure is represented by the following formula (la), and two hydrogen atoms bonded to one of the carbon atoms adjacent to the oxygen atom in the formula (la) may be substituted with an oxygen atom to form a general formula (lb) represents a cyclic structure; R12 is a hydrocarbon group having 1 to 5 carbon atoms or an organic compound represented by the following formula (lc), (Id), (le), (If), (lg) or (lh) Base; 317388 57 1266752 [chemical i] h2c——0, (la) H2xCx—〇〆 (where x is an integer from 1 to 7), [Chemical 2] 0=c—(lb) H2yCv- (where y Is an integer from 1 to 7), [Chemical 3] 0 II (lc) —0—C—CpH2p+1 (where P is an integer from 4 to 30), φ [Chemical 4] 〇II 〇—Γ 0H 0-CqH0-CqH (Id) (其中，q為4至30之整數）， 58 317388 1266752 [化5] Ο -Ο——Ρ——Cq ·Η2ς (le) (其中，q’為4至30之整數）， [化6] OCrH2rNHCr fNH2 (其中，r及r’各別為1以上之整數，r+r’為4至30之整 數）， [化7](Id) (where q is an integer from 4 to 30), 58 317388 1266752 [化5] Ο -Ο——Ρ——Cq ·Η2ς (le) (where q' is an integer from 4 to 30), [ 6] OCrH2rNHCr fNH2 (wherein r and r' are each an integer of 1 or more, and r+r' is an integer of 4 to 30), [Chem. 7] (lg) ❿ （其中’s為1至30之整數）’ [化8](lg) ❿ (where 's is an integer from 1 to 30)' [Chem. 8] (其中，t及t’分別為1至30之整數）]; R21TiR22R232 ...........(2) [式中，R21為碳原子數1至4之烷氧基，R22為下述通 59 317388 1266752 · 式（2a)表示之有機基，R23為下述通式（2b)表示之有機 基； [化9] 〇 II υ+1 (2 a) C'CuH2l (其中’u為4至30之整數） [化 10] O R，II 0——C 2 (2b) 中.，R’為氫原子或碳原子數丨至4之烧基; R 4Τι · [p(〇C2wH2w+1)2(〇H^2 ...........⑶ 碳原子數1 i 2G之燒氧基，該烧氧基中 SI::部分可經碳原子數為4至12且具㈣鍵及 雙鍵中之至少一者之有機基取代； w為4至20之整數]。 3·如申請專利範圍第1 # 貝之3有鈦之矽溶膠，其中，構成 上述二虱化鈦微粒子及多孔曾— 卜m缺此/ 夕札貝—虱化矽微粒子（al)或經 述鈦化合物進行表面修 化矽微粒子（a2)之矽及鈦之含 夕孔貝一乳 a卜卜 里以Sl〇2/Ti09曹晉比 換算，係在5至2U00之範圍。 2/ 2重里比 4·如申請專利範圍第丨項之含有 多；f丨所-β 有欽之石夕溶膠，其中，上述 夕孔貝一氧化矽微粒子之表面 电何里為母lg該微粒子 317388 60 1266752 在10至150//eq之範圍内。 •=申明專利範圍第1項之含有鈦之矽溶膠，其中，上述 多孔質二氧切微粒子係將溶膠狀之H厂氧化= 二：= 夕微粒子表面用二氧切包覆，接著進行脫銘 k理而形成。 6. -種含有鈦之♦溶膠（als)之製造方法，該含有鈦之石夕容 =(叫包括：平均粒徑為2至5_之二氧化欽微粒 子，平均粒徑為5至100nm，經由BET法求得之比表 面積在3GGmVg以上之多孔質二氧切微粒子⑽广 及分散溶劑（b);該製造方法係將：由平均粒徑為2至 5〇nm之二氧化鈦微粒子及分散溶師)組成之欽溶膠； 與平均粒徑為5至1(K)nm，經由贿法求得之比表面 Srt、:0!·、111 以上之多孔質二氧化矽微粒子及分散溶 Μ (b)、、且成之石夕溶膠予以混合。 7. 二種含有鈦之石夕溶膠（a2s)之製造方法，該含有欽之石夕溶 少（2S)中平均粒控為5至100nm ’經由BET法求得 之^面積在3GGmVg以上之多孔質：氧切微粒子 =表面由鈦酸酉旨系化合物㈣及分散溶劑⑻所組成；該 衣造方法之特徵為：在包括平均粒徑為&amp; 1〇〇，經 由BET法求得之比表面積在300m2/g以上之多孔質二 # /夕U粒子及分散溶劑（b)組成之矽溶膠中，添加鈦酸 酉旨糸化合物。 種抗污被膜形成用組成物，係在如申請專利範圍第1 項之含有鈦之石夕溶膠中分散黏合劑（c)而成者。 317388 61 1266752 ., 9. 種墨水接文層形成用塗佈液，係在如申請專利範圍第 1項之含有鈦之矽溶膠中分散黏合劑（c，）而成者。 10. 如申請專利範圍第9項之墨水接受層形成用塗佈液，其 中，該塗佈液係含有··上述微粒子（al)或上述微粒子 (a2)100重量份、及上述黏合劑（c，）5至7重量份， 上述分散溶劑（b)之重量（Wb)，與上述微粒子（al) 或上述微粒子（a2)及上述黏合劑（c，）之合計重量 (wA+wc)之比為 Wb : (Wa+Wc)=99 9 至 5〇: 〇 】至％[但 &gt; 是，合計為1〇〇] 構成上述微粒子（al)或上述微粒子（a2)之矽及鈦之 含罝，以Si〇2/Ti〇2重量比換算，為在5至21，〇〇〇之 範圍。 11·一種如申請專利範圍第9項之墨水接受層形成用塗佈 液之製造方法，其中，將下述成分加以混合： 由上述微粒子（al)分散於上述分散溶劑（b)所成之 ，含有鈦之矽溶膠（als)、 上述黏合劑（c，）、及 依需要而添加之上述分散溶劑（b)。 12· —種如申請專利範圍第9項之墨水接受層形成用塗佈 液之製造方法，其中，將下述成分加以混合： 由上述微粒子（a2)分散於上述分散溶劑（b)所成之 含有鈦之矽溶膠（a2s)、 上述黏合劑（c’）、及 依需要而添加之上述分散溶劑（b)。 317388 62 j 1266752 —— Μ 13. —種附有墨水接受層之記錄用基 成含有下列⑽或㈣之墨水接受層者麵基材表面形 (al):平均粒徑為2至5-之二氧化鈦微粒子及 在300m 以上之多孔質二氧化矽微粒子或， (a2).平均粒徑為5至1〇〇nm，經由扯τ法 :表面積在w/g以上之多孔質二氧化石夕微粒； 表面以鈦酸酯系化合物進行表面修飾所成之多 零氧化矽微粒子。 貝— 14. -種申請專利範圍第13項之附有墨水接受層之 &quot;ί材之製造方法’其中，絲基材表面塗佈㈣請專利 乂, 觀圍第9項之墨水接受層形成用塗佈液後，進行乾燥 15. —種記錄用基材之再生方法，其係在如申請專利範圍第 13項之附有墨水接受層之記錄用基材上，用墨水進行 刷，形成印字或印圖後，經由紫外線照射、與酸性氣體 • 或臭氧接觸而進行該印字或印圖之消色。 水一 317388 63(wherein t and t' are each an integer from 1 to 30)]; R21TiR22R232 (2) [wherein R21 is an alkoxy group having 1 to 4 carbon atoms, R22 The following is an organic group represented by the formula (2a): R23 is an organic group represented by the following formula (2b); [Chem. 9] 〇II υ +1 (2 a) C'CuH2l (where ' u is an integer from 4 to 30) OR, II 0 - C 2 (2b), R' is a hydrogen atom or a carbon atom of 丨 to 4; R 4Τι · [p(〇C2wH2w +1)2(〇H^2 ..... (3) Alkoxy group having 1 to 2 carbon atoms, wherein the SI:: moiety in the alkoxy group may have a carbon number of 4 to 12 And having an organic group substitution of at least one of the (four) bond and the double bond; w is an integer of 4 to 20] 3. As claimed in the patent claim 1 #贝之3, there is a titanium sol, wherein the above two 构成Titanium granules and porous granules - 卜m lack this / 夕札贝 - 虱 矽 矽 矽 ( al al al al al 或 或 或 或 或 al al al al al al al al al al al 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽Bu Li is converted to S1〇2/Ti09 Cao Jinbi, which is in the range of 5 to 2U00. 2/ 2 重比比4·如申Please refer to the 专利 丨 ; ; ; ; ; ; ; ; ; ; ; ; , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 317 317 317 317 317 317 317 317 Within the range of /eq. • = the titanium-containing cerium sol of claim 1 of the patent scope, wherein the porous oxidized microparticles are oxidized in the sol-like H plant = 2: = the surface of the granules is diced with dioxane The coating is then formed by removing the ing. 6. A method for producing a sol containing titanium, which contains a titanium stone (including: an average particle diameter of 2 to 5 _ oxidized) The porous microparticles have an average particle diameter of 5 to 100 nm, and the porous dioxygen microparticles (10) having a specific surface area of 3 GGmVg or more and a dispersion solvent (b) obtained by a BET method; the production method is: an average particle diameter of 2 a sol consisting of titanium dioxide microparticles and dispersion sols of 5 〇 nm; and a porous material having an average particle diameter of 5 to 1 (K) nm and having a specific surface Srt, 0:·, 111 or more by bribery The cerium oxide microparticles and the dispersed cerium (b), and the cerium sol are mixed 7. A method for producing two kinds of titanium-containing sols (a2s) containing an average particle size of 5 to 100 nm in the case of a small amount of (2S), which is obtained by the BET method, and has an area of 3 GGmVg or more. Porous: oxygen-cut microparticles = surface composed of barium titanate-based compound (IV) and dispersing solvent (8); the coating method is characterized by including a ratio of average particle diameter &amp; A barium titanate ruthenium compound is added to the ruthenium sol having a surface area of 300 m 2 /g or more and a porous granule of the dispersion medium (b). The anti-fouling film-forming composition is obtained by dispersing a binder (c) in a Titanium-containing sol containing titanium according to the first aspect of the patent application. 317388 61 1266752 . 9. A coating liquid for forming an ink contact layer, which is obtained by dispersing a binder (c,) in a titanium-containing cerium sol according to claim 1 of the patent application. 10. The coating liquid for forming an ink receiving layer according to the ninth aspect of the invention, wherein the coating liquid contains 100 parts by weight of the fine particles (al) or the fine particles (a2), and the binder (c) , 5 to 7 parts by weight, the weight (Wb) of the dispersion solvent (b), and the total weight (wA + wc) of the fine particles (al) or the fine particles (a2) and the binder (c,) Wb : (Wa + Wc) = 99 9 to 5 〇: 〇] to % [but &gt; Yes, total 1 〇〇] constitutes the above-mentioned fine particles (al) or the above-mentioned fine particles (a2) and the inclusion of titanium In terms of Si〇2/Ti〇2 weight ratio, it is in the range of 5 to 21, 〇〇〇. A method for producing a coating liquid for forming an ink receiving layer according to claim 9, wherein the following components are mixed: the fine particles (al) are dispersed in the dispersion solvent (b), A titanium-containing sol (als), the above-mentioned binder (c), and the above-mentioned dispersion solvent (b) added as needed. The method for producing a coating liquid for forming an ink receiving layer according to the ninth aspect of the invention, wherein the following components are mixed: the fine particles (a2) are dispersed in the dispersion solvent (b) A titanium-containing cerium sol (a2s), the above-mentioned binder (c'), and the above-mentioned dispersion solvent (b) added as needed. 317388 62 j 1266752 - Μ 13. - Recording base with ink receiving layer containing the following (10) or (4) ink receiving layer surface of the substrate surface (al): titanium dioxide fine particles having an average particle diameter of 2 to 5 And porous cerium oxide microparticles of 300 m or more or (a2). The average particle diameter is 5 to 1 〇〇 nm, via the τ method: porous SiO2 particles having a surface area of w/g or more; The titanate compound is subjected to surface modification to form a plurality of zero cerium oxide microparticles. — - 14. - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - After drying with a coating liquid, a method for regenerating a substrate for recording is applied to a substrate for recording having an ink receiving layer as disclosed in claim 13 of the patent application, and is brushed with ink to form a printing. Or after printing, the printing or printing is achromatic by ultraviolet light irradiation, contact with acid gas or ozone. Water one 317388 63
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